CN112839966A - Process for olefin polymerization using alkane soluble non-metallocene precatalyst - Google Patents

Abstract

A process for polymerizing olefin monomers to produce a polyolefin composition comprising a polyolefin polymer, the process comprising: contacting a solution of an alkane-soluble non-metallocene pre-catalyst dissolved in an alkane solvent with an activator to produce a trimmed catalyst comprising an alkane-soluble non-metallocene catalyst; feeding the trim catalyst to a polymerization reactor as a solution in an alkane solvent or a dry powder supported on a support material or a slurry thereof in an alkane solvent; and polymerizing the olefin monomer with the trim catalyst in the polymerization reactor to produce the polyolefin composition.

Description

Process for olefin polymerization using alkane soluble non-metallocene precatalyst

Technical Field

Catalyzing the polymerization of olefins.

Publications and patents in or relating to this field include US20050182210a1, US20180002464a1, US20180079836a1, US5318935, US5506184, US5889128, US6255419B1, US6274684B1, US6534604B2, US6841631B2, US6858684B2, US6894128B2, US6949612B2, US6967184B2, US6995217B2, US7163991B2, US7196032B2, US7276566B2, US7479529B2, US7566677B2, US7718566B2, US7754840B2, US7973112B2 and US9902790B 2. US6967184B2 mentions the synthesis of HN5Zr (NMe2) 2. US20180002464a1 mentions biphenol precatalysts ("procatalysts", e.g. compounds 1 to 7 of paragraph [0104 ]). US7973112B2 mentions a spray-dried catalyst containing bis (benzyl) [ N '- (2,3,4,5, 6-pentamethylphenyl) -N- [2- (2,3,4,5, 6-pentamethylphenyl) amino- κ N ] ethyl ] -1, 2-ethane-diamino (2-) κ N, κ N' ] zirconium or "HN 5 Zr" (herein referred to simply as "HN 5Zr dibenzyl") and (N-propylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride. US6858684B2, US6949612B2, US6995217B2 and US20180079836a1 mention catalyst transitions.

Introduction to the word

We describe solutions to one or more problems relating to polymerizing olefin monomers with a bimodal catalyst system comprising a Higher Molecular Weight (HMW) catalyst made from a non-metallocene alkane insoluble precatalyst (e.g., HN5Zr dibenzyl) and an activator, and a Lower Molecular Weight (LMW) metallocene catalyst made from polyethylene (MCN). The bimodal catalyst system produces a bimodal polyethylene composition comprising a HMW polyethylene component and a LMW polyethylene component in a single reactor. Some of the problems relate to the undesirable gelling in the post-reactor melt blended bimodal polyethylene composition. Other problems relate to the transitional complexity and stability of bimodal catalyst systems.

Bimodal catalyst systems comprise or are made from a Metallocene (MCN) precatalyst, an alkane-insoluble non-metallocene precatalyst ("insoluble non-MCN" precatalyst), at least one activator, and a support material (solid). An insoluble non-MCN precatalyst (e.g., HN5Zr dibenzyl) makes the HMW polyethylene component of the bimodal polyethylene composition. The MCN pre-catalyst is soluble in the alkane, and the MCN catalyst produces the LMW polyethylene component of the bimodal polyethylene composition. Gel problems can occur if the insoluble non-MCN pre-catalyst and its activator are fed into the polymerization reactor separately from the MCN pre-catalyst and its activator. The resulting HMW polyethylene component and LMW polyethylene component will then first be made separately in the reactor and may not be uniformly mixed together thereafter. This may result in a comparative bimodal polyethylene composition having an undesirable increase in gel content, where the gel is composed of a portion of the HMW polyethylene component. The gel content of the comparative bimodal polyethylene composition may be too high for applications requiring clarity such as films and/or for applications requiring high strength such as pipes.

To reduce or avoid the gelling problem, bimodal catalyst systems are formulated in two parts. The first part comprises a slurry of the support, the alkane solvent, at least one activator, all insoluble non-MCN pre-catalyst and some MCN pre-catalyst. The second part comprises a solution of the remainder of the MCN precatalyst in the alkane solvent, but does not comprise an insoluble non-MCN precatalyst, activator or support. In the "split-mix" feed process, the first and second fractions are fed separately into an in-line mixer where they are mixed to produce a bimodal catalyst system. The fresh bimodal catalyst system is fed into a single polymerization reactor.

The partial blend feed process has some flexibility to achieve a variety of polymerization rates and is capable of producing a variety of bimodal polyethylene compositions with a variety of polymer characteristics in a single polymerization reactor. For example, the flow rate of the feed of the second fraction may be adjusted to supplement the effect of the portion of MCN pre-catalyst in the first fraction (e.g., to produce more LMW polyethylene component), or to "trim" or adjust the effect of the insoluble non-MCN pre-catalyst of the first fraction (e.g., to increase the LMW/HMW ratio), thereby enabling the production of various bimodal polyethylene compositions. Thus, the second part is referred to as the "trim catalyst". The partial blend feed process allows control over the polymerization reaction producing the bimodal polyethylene composition and variation in the LMW/HMW ratio to transition between the various bimodal polyethylene compositions in a single polymerization reactor.

The first part beneficially contains all insoluble non-MCN pre-catalyst, activator and some MCN pre-catalyst and is premixed with the desired amount of the second part (trim catalyst) to produce a bimodal catalyst system prior to entering the polymerization reactor. This is done in order to form the HMW polyethylene component and the LMW polyethylene component into a so-called reaction blend in the polymerization reactor, such that the HMW polyethylene component and the LMW polyethylene component are in intimate contact with each other in situ. The reactor blend allows for better mixing of the HMW polyethylene component and the LMW polyethylene component in the bimodal polyethylene composition, thus reducing the gel content.

Unfortunately, in the split mixed feed process, the HMW/LMW ratio cannot be zero or close to zero, since the first fraction of the bimodal catalyst system comprises both MCN pre-catalyst and insoluble non-MCN pre-catalyst, and thus the bimodal polyethylene composition thereby always comprises an amount of LMW polyethylene component and HMW polyethylene component.

Furthermore, the transition between bimodal catalyst systems ("catalyst transition") such as between different pre-catalysts or between different amounts of the same pre-catalyst in a single polymerization reactor is complicated. For example, the transition from a first bimodal catalyst system comprising a first MCN catalyst (abbreviated LMW-CAT-1) and a first insoluble non-MCN pre-catalyst to a second bimodal catalyst system comprising a second MCN catalyst (abbreviated LMW-CAT-2) and the same first insoluble non-MCN pre-catalyst is complex, wherein LMW-CAT-1 and LMW-CAT-2 are different from each other and from the insoluble non-MCN pre-catalyst. Even if the insoluble non-MCN pre-catalyst in the first portion of both the first bimodal catalyst system and the second bimodal catalyst system is the same, the first portion and the second portion of the first bimodal catalyst system must be replaced in order to transition to the second bimodal catalyst system. This is because both the first and second fractions contain LMW-CAT-1 components that are no longer required.

Moreover, certain insoluble non-MCN precatalysts become unstable after mixing with the activator. Those first portions of the bimodal catalyst system, including the unstable/insoluble non-MCN pre-catalyst, must be cooled to about-10 degrees celsius (° c) for shipping or storage. The second part may then need to be reconfigured to withstand the cooling "shock" when it contacts the cooled first part in the in-line mixer. Or the first portion may need to be heated before feeding it to the in-line mixer.

Also, since insoluble non-MCN precatalysts are insoluble in alkanes, they are not suitable for use in the second part (trim catalyst) of the split-mix feed process.

Disclosure of Invention

A process for polymerizing olefin monomers to produce a polyolefin composition, the process comprising: contacting a solution of an alkane-soluble non-metallocene pre-catalyst dissolved in an alkane solvent with an activator to produce a trimmed catalyst comprising an alkane-soluble non-metallocene catalyst; feeding the trim catalyst to a polymerization reactor as a solution in an alkane solvent or a dry powder supported on a support material or a slurry thereof in an alkane solvent; and polymerizing an olefin monomer with the trim catalyst in the polymerization reactor to produce the polyolefin composition.

Drawings

FIG. 1 is a Gel Permeation Chromatogram (GPC) of a bimodal polyethylene composition produced according to the method of inventive example 9A.

Figure 2 contains structural formulas of some embodiments of alkane-soluble non-metallocene precatalyst.

Figure 3 contains structural formulas of some embodiments of intermediates used to synthesize embodiments of the alkane soluble non-metallocene precatalyst of figure 2.

Figure 4 contains the structural formula of one embodiment of a biphenol precatalyst as an example of an alkane soluble non-metallocene precatalyst.

Detailed Description

The summary, claims and abstract are incorporated herein by reference. Certain aspects and embodiments are described and numbered below to facilitate cross-reference.

Aspect 1.a process for polymerizing olefin monomers to produce a first polyolefin composition comprising a first polyolefin polymer, the process comprising steps (a) to (C): (A) contacting a solution of a first alkane-soluble non-metallocene precatalyst (abbreviated as first ASNM precatalyst) dissolved in an alkane solvent with an activator (e.g., in a mixer apparatus such as an in-line mixer apparatus or a catalyst mixing tank) or in a conduit, such as by feeding the solution of the first ASNM precatalyst through a first conduit and feeding the activator (e.g., as a slurry of the alkane solvent) through a second conduit to a junction (e.g., a "Y" or "T" junction) where the first conduit and the second conduit are combined into one conduit) to produce a first trim catalyst comprising the first alkane-soluble non-metallocene catalyst (abbreviated as first ASNM catalyst); (B) feeding a first trim catalyst to a polymerization reactor; and (C) polymerizing olefin monomer with the first trim catalyst in a polymerization reactor; thereby preparing a first polyolefin composition comprising a first polyolefin polymer; wherein the first ASNM precatalyst is characterized by comprising at least 60 wt% based on the total weight of the ASNM precatalyst and hexaneN-hexane (CH)₃(CH₂)₄CH₃) The solubility in hexane of (a) is at least 0.10 weight percent (wt%), as measured using the solubility test method (enhanced solubility). In contrast, the insoluble pre-catalyst comprised at least 60 wt% n-hexane (CH) based on the total weight of the insoluble pre-catalyst and hexane₃(CH₂)₄CH₃) Has a solubility in hexane of from 0.00 wt% to 0.099 wt%, as measured using the solubility test method. Step (B) may be performed after and/or during step (a). Step (C) may be performed after and/or during step (B). The first trim catalyst is the product of the reaction of a first alkane-soluble non-metallocene pre-catalyst with an activator. The olefin may be fed to the polymerization reactor at once, intermittently (e.g., periodically), or continuously. The first polyolefin polymer can be removed from the polymerization reactor once, intermittently (e.g., periodically), or continuously. The first polyolefin composition may be unimodal (consisting essentially of the first polyolefin polymer) or multimodal (consisting essentially of the first polyolefin polymer and at least one second polyolefin polymer different from the first polyolefin polymer). The first polyolefin polymer may be a Higher Molecular Weight (HMW) polyolefin. In some aspects, the process and reactor are free of metallocene (pre) catalysts. In some aspects, the methods and reactors further comprise the use of a first metallocene (pre) catalyst. By (pre) catalyst is meant a pre-catalyst, a catalyst, or both. The activator may be an alkylaluminoxane or a trialkylaluminium compound.

Aspect 2. the process of aspect 1, wherein the first trim catalyst comprises a solution of the first ASNM catalyst dissolved in an alkane solvent, and step (B) comprises feeding the solution to the reactor, the solution being free of support material (finely divided solids). The alkane solvent of the feeding step may be the same as or different from the alkane solvent used in the contacting step. When the solvents are different, the method may further comprise a solvent exchange or replacement step.

Aspect 3. the method of aspect 1 or 2, further comprising steps (a) and (b): (a) separately from step (a), contacting a first metallocene precatalyst with an activator and optionally a support material to prepare a first metallocene catalyst, the first metallocene catalyst optionally being located on and/or in the support material; and (B) feeding the first metallocene catalyst to the polymerization reactor separately from step (B); and wherein step (C) further comprises polymerizing olefin monomer with the first metallocene catalyst in a polymerization reactor; thereby preparing a first bimodal polyolefin composition comprising a first polyolefin polymer and a second polyolefin polymer. The second polyolefin polymer is prepared from the first metallocene catalyst and is different from the first polyolefin polymer prepared from the trim catalyst. The activator of step (a) may be the same as or different from the activator of step (a). The first metallocene catalyst is the product of the reaction of a first metallocene precatalyst with the activator of step (a). In some aspects, the support material is not present, alternatively is present in the first trim catalyst. In some aspects, the support material is absent, alternatively present in the first metallocene catalyst. The support material may independently be untreated silica, alternatively calcined untreated silica, alternatively silica treated with a hydrophobic agent, alternatively silica treated with a calcined and hydrophobic agent. The hydrophobing agent may be dichlorodimethylsilane.

Aspect 4. the method of aspect 3, wherein step (B) comprises feeding the first trim catalyst to the polymerization reactor as a solution of the first ASNM catalyst dissolved in the first alkane solvent; and step (b) comprises separately feeding a solution of the first metallocene catalyst dissolved in a second alkane solvent to the polymerization reactor; wherein the first alkane solvent is the same or different from the second alkane solvent; and wherein the solution is free of support material. By separately fed is meant that the solutions enter the polymerization reactor through different injector means at the same time or through the same injector means at different times.

Aspect 5. the method of aspect 3 or 4, further comprising, after step (C), (D) transitioning the method from steps (a) and (b) to steps (a1) and (b1), respectively: (a1) contacting a second metallocene precatalyst, which is different from the first metallocene precatalyst, with an activator and optionally a support material in order to prepare a second metallocene catalyst, which is different from the first metallocene catalyst in the structure of the at least one cyclopentadienyl ligand, wherein the second metallocene catalyst does not contain a support material or is located on and/or in a support material; and (b1) decreasing the feed of the first metallocene catalyst from the steady state value until the first metallocene catalyst is no longer fed to the polymerization reactor, and independently starting and increasing the feed of the second metallocene catalyst to the polymerization reactor until the second metallocene catalyst is fed to the polymerization reactor at the steady state value; and wherein step (C) further comprises polymerizing olefin monomer with a second metallocene catalyst in the polymerization reactor; thereby producing a second multimodal (e.g. bimodal) polyolefin composition comprising a first polyolefin polymer produced by the first trim catalyst and a third polyolefin polymer produced by the second metallocene catalyst, wherein the third polyolefin polymer is different from each of the first and second polyolefin polymers. The first multimodal polyolefin composition may be removed from the polymerization reactor during step (D) such that the final polymerization reactor no longer comprises the first multimodal polyolefin composition and only the second multimodal polyolefin composition. Thus, the transition includes both catalyst transition characteristics and polymer transition characteristics. The activating agent of step (a1) may be the same as or different from the activating agent of step (a). The second metallocene catalyst differs in structure from the first metallocene catalyst in the structure of the cyclopentadienyl ligand. For example, the first metallocene catalyst may have at least one unsubstituted cyclopentadienyl ligand, and the second metallocene catalyst may have two identical or different substituted cyclopentadienyl ligands and no unsubstituted cyclopentadienyl ligand. Alternatively, the first metallocene catalyst may have a methylcyclopentadienyl ligand and a butylcyclopentadienyl ligand, and the second metallocene catalyst may have a methylcyclopentadienyl ligand and a propylcyclopentadienyl ligand.

Aspect 6 the method of aspect 1, wherein the first trim catalyst further comprises a support material having the first ASNM catalyst disposed thereon.

Aspect 7.a method for polymerizing an olefin monomer to produceA process for a first bimodal polyolefin composition comprising a first Higher Molecular Weight (HMW) polyolefin component and a first Lower Molecular Weight (LMW) polyolefin component, the process comprising steps (1) to (5): (1) contacting a solution of a first alkane-soluble non-metallocene pre-catalyst (first ASNM pre-catalyst) dissolved in an alkane solvent with an activating agent (e.g., in a mixer device or a pipe) to produce a first trim catalyst comprising the first alkane-soluble non-metallocene catalyst (first ASNM catalyst); (2) contacting a first metallocene precatalyst and an additional amount (a first additional amount) of a first alkane-soluble non-metallocene precatalyst (a mixture thereof) with an activator and optionally a support material (e.g., in a mixer apparatus or a pipe) to prepare a first bimodal catalyst system comprising the first metallocene catalyst and the additional amount of a first ASNM catalyst, the first bimodal catalyst system optionally being free of support material or being located on and/or in support material; (3) contacting the first bimodal catalyst system with a first trim catalyst (e.g., in a first mixer apparatus (e.g., a first in-line mixer apparatus) or in a first conduit) to produce a first mixed catalyst system comprising a mixture of the first bimodal catalyst system and the first trim catalyst; (4) feeding a first mixed catalyst system to a polymerization reactor; and (5) polymerizing olefin monomers with the first mixed catalyst system in the polymerization reactor; thereby producing a first HMW polyolefin component and a first LMW polyolefin component of the first bimodal polyolefin composition; wherein the first ASNM pre-catalyst is characterized by comprising at least 60 wt% n-hexane (CH) based on the total weight of the first ASNM pre-catalyst and hexane₃(CH₂)₄CH₃) Has a solubility in hexane of at least 0.10 wt%, as measured using the solubility test method.

Aspect 8. the method of aspect 7, further comprising, after step (5), (6) transitioning the method from steps (2) to (5) to steps (2a) to (5a), respectively: (2a) contacting (e.g., in a mixer apparatus such as a third catalyst tank or in a pipeline) the second metallocene precatalyst and the second additional amount of the first alkane-soluble non-metallocene precatalyst with the activator and the optional support material to produce a second bimodal catalyst system comprising the second metallocene catalyst and the second additional amount of the first ASNM catalyst, the second bimodal catalyst system optionally being free of support material or being located on and/or in support material; (3a) contacting the second bimodal catalyst system with a first trim catalyst (e.g., in a second mixer apparatus (e.g., a second in-line mixer apparatus, which may be the same or different from the first in-line mixer apparatus) or in a second conduit (which may be the same or different from the first conduit)) to produce a second mixed catalyst system comprising a mixture of the second bimodal catalyst system and the first trim catalyst; (4a) decreasing the feed of the first mixed catalyst system from a steady state value until the first mixed catalyst system is no longer fed to the polymerization reactor, and independently starting and increasing the feed of the second mixed catalyst system to the polymerization reactor until the second mixed catalyst is fed to the polymerization reactor at the steady state value; and (5a) polymerizing olefin monomers with the second mixed catalyst system in the polymerization reactor; thereby producing a second bimodal polyolefin composition comprising a first HMW polyolefin component and a second LMW polyolefin component, the second LMW polyolefin component being different from each of the first HMW polyolefin component and the first LMW polyolefin component. The first bimodal polyolefin composition can be removed from the polymerization reactor during step (6) such that the final polymerization reactor no longer contains the first bimodal polyolefin composition and only contains the second bimodal polyolefin composition. Thus, the transition includes both catalyst transition characteristics and polymer transition characteristics.

Aspect 9. the method of any one of aspects 1 to 8, wherein the olefin monomer is any one of (i) to (vii): (i) ethylene; (ii) propylene; (iii) (C)₄-C₂₀) Alpha-olefins, alternatively (C)₄-C₈) An alpha-olefin, alternatively 1-butene, alternatively 1-hexene, alternatively 1-octene; (iv)1, 3-butadiene; (v) (iii) a combination of (i) and (ii); (vi) (iv) a combination of (i) and (iii); and (vii) combinations of (i), (ii), and (iv); and wherein the first polyolefin polymer or HMW polyolefin component (as the case may be) comprises any of (a) to (g), respectively: (a) a polyethylene homopolymer; (b) a polypropylene homopolymer; (c) poly(s) are polymerized(C₄-C₂₀) An alpha-olefin polymer; (d) a polybutadiene polymer; (e) ethylene-propylene copolymers; (f) poly (ethylene-co- (C)₄-C₂₀) Alpha-olefin) copolymers; and (g) an ethylene-propylene-butadiene copolymer. The method may comprise (i) and (a), alternatively (vi) and (f).

Aspect 10. the method of any of aspects 1 to 9, wherein the first polyolefin polymer or HMW polyolefin component (as the case may be) has a weight average molecular weight of at least 110,000 grams per mole (g/mol), alternatively from 130,000g/mol to 1,900,000g/mol, alternatively from 150,000g/mol to 990,000 g/mol.

Aspect 11. the method of any one of aspects 1 to 10, wherein the polymerization is a gas phase polymerization process and the polymerization reactor is a single gas phase polymerization reactor (e.g., a fluidized bed gas phase polymerization reactor). In other aspects, the process uses two polymerization reactors, wherein the first HMW polyolefin component is produced in the first polymerization reactor from a first ASNM catalyst and the first LMW polyolefin component is produced in the second polymerization reactor from a first metallocene catalyst, or vice versa.

Aspect 12. the method of any one of aspects 1 to 11, further comprising (D1) transitioning from step (B) to step (B1), feeding a second trim catalyst to the polymerization reactor, the second trim catalyst being prepared by contacting a solution of a second alkane-soluble non-metallocene precatalyst (second ASNM precatalyst) dissolved in an alkane solvent with an activator to prepare a second alkane-soluble non-metallocene catalyst (second ASNM catalyst); wherein the second ASNM precatalyst is different from the first ASNM precatalyst in the structure of the at least one non-metallocene ligand and the second ASNM catalyst is different from the first ASNM catalyst in the structure of the at least one non-metallocene ligand; wherein the second ASNM precatalyst is characterized by a solubility in hexane comprising at least 60 wt.% n-hexane of at least 0.10 wt.%, based on the total weight of the second ASNM precatalyst and hexane, as measured using the solubility test method; and wherein transitioning comprises decreasing the feed of the first trim catalyst from the steady state value until the first trim catalyst is no longer fed to the polymerization reactor, and independently starting and increasing the feed of the second trim catalyst to the polymerization reactor until the second trim catalyst is fed to the polymerization reactor at the steady state value. Tailoring the catalyst transition is useful for transitioning from a steady state polymerization process that produces a first stage polyolefin polymer to another steady state polymerization process that produces another stage polyolefin polymer. The second ASNM precatalyst differs from the first ASNM precatalyst in the structure of at least one non-metallocene ligand. For example, a first ASNM precatalyst may have a ligand of formula (1) described later, and a second ASNM precatalyst may have a biphenol ligand described later. Alternatively, the first and second ASNM precatalysts may have different ligands of formula (1) described later.

Aspect 13. the method of any of aspects 1 to 12, wherein each of the ASNM precatalysts is independently characterized by the inclusion of at least 60 wt.% n-hexane (CH)₃(CH₂)₄CH₃) The hexane has a solubility in hexane of 0.10 wt% to 25 wt%, alternatively 0.50 wt% to 24 wt%, alternatively 1.0 wt% to 25 wt%, alternatively 2.0 wt% to 25 wt%, alternatively 3.0 wt% to 25 wt%, alternatively 5.0 wt% to 25 wt%, alternatively 10.0 wt% to 25 wt%, alternatively 15 wt% to 25 wt%, alternatively 20.0 wt% to 25 wt%, alternatively 0.10 wt% to 20.0 wt%, alternatively 0.5 wt% to 20.0 wt%, alternatively 1 wt% to 15 wt%, alternatively 2 wt% to 15 wt%, alternatively 3 wt% to 15 wt%, alternatively 5 wt% to 15 wt%, alternatively 1.0 wt% to 10.0 wt%, as measured using a solubility test method. Advantageously, the solubility of the ASNM precatalyst in hexane comprising at least 60 wt% n-hexane is enhanced relative to that of HN5Zr dibenzyl, the latter having a solubility in hexane comprising at least 60 wt% n-hexane of only 0.03 wt%, as measured by the solubility test method.

The catalyst transition includes decreasing the first catalyst feed from a steady state value to an off (stopped) state and increasing the second catalyst (different) feed from an off (not started) state to a steady state value. The decrease and increase may be performed independently, continuously or intermittently (e.g., periodically, such as stepwise increases); may begin at the same time or at different times; can be done at the same time or at different times; and may take the same length of time or a different length of time. Typically, the time taken for the decreasing step overlaps the time taken for the increasing step by at least 50%, alternatively 79% to 100%, alternatively 91% to 100%. The time at which the transition period begins is the first of the beginning of the decreasing step or the beginning of the increasing step. The time at the end of the transition period is the later one of the end of the decrease step (0 feed) or the end of the increase step (steady state feed). A typical transition period may be 1 to 48 hours, alternatively 2 to 24 hours, alternatively 3 to 12 hours.

Catalyst transitioning can also optionally include changing one or more other process conditions, such as reactor temperature, (co) monomer flow rate, superficial gas velocity within the reactor, and/or the rate at which polymer product is removed from the reactor in a continuous reactor (rather than a batch reactor).

The catalyst transition may be carried out in a "closed" polymerization reactor, which means that the reactor is not shut down or stopped during the transition. Shutting down a polymerization reactor generally refers to opening the reactor, purging hydrocarbons from the open reactor with a purge gas (e.g., nitrogen), evacuating polymer and catalyst particles from the purged reactor, and purging the evacuated reactor. Alternatively or additionally, the catalyst transition may be conducted without introducing a catalyst "kill" agent or a polymerization neutralizing agent into the reactor.

The catalyst transition is useful for transitioning between different stages (first and second stages) of the same polyolefin composition or between different polyolefin polymers (first and second polymers). During the transition, an intermediate stage of polymer can be produced that is different from the steady state stages of the start and transition. The intermediate stage polymer may have its own use or a small portion thereof may be melt blended with other polymers to make useful post-reactor polymer blends.

The process can be used in solution phase, slurry phase or gas phase polymerization reactions. The polymerization reactor may be a reactor configured for solution phase, slurry phase or gas phase polymerization of at least one olefin monomer. Reactors and effective polymerization conditions for solution phase, slurry phase or gas phase polymerization are well known.

In some aspects, the process comprises a gas phase polymerization and a gas phase polymerization reactor (e.g., a fluidized bed gas phase polymerization reactor), and the olefin monomer comprises ethylene and optionally 1-butene, 1-hexene, or 1-octene. In certain aspects, the method is free of Cr, Ti, Mg, or unsubstituted or substituted cyclopentadienyl groups; alternatively Cr, Ti and Mg; alternatively unsubstituted or substituted cyclopentadienyl groups.

Alkane soluble non-metallocene precatalyst (ASNM precatalyst)

The alkane-soluble non-metallocene precatalyst (ASNM precatalyst) may be any compound lacking an unsubstituted or substituted cyclopentadienyl group; and is characterized by containing at least 60% by weight of n-hexane (CH) based on the total weight of ASNM pre-catalyst and hexane₃(CH₂)₄CH₃) Has a solubility in hexane of at least 0.10 wt%, as measured using the solubility test method (enhanced solubility); and converted by the activator to a catalyst effective to polymerize olefin monomers. The ASNM precatalyst may include aprotic solvates and solvent-free embodiments thereof. In any of the preceding aspects, the ASNM precatalyst may be any of those described in the following numbered embodiments and examples.

Embodiment 1.ASNM precatalyst may be any of the diphenol precatalysts described in paragraphs [0036] to [0080] and [0104] US20180002464a1, alternatively paragraph [0080] US20180002464a1, alternatively US20180002464a1, paragraph [0104], alternatively the diphenol precatalyst (5) of figure 4. In some aspects, the biphenol precatalyst is a compound characterized by a solubility in hexane comprising at least 60 wt% n-hexane of from 0.10 wt% to 25 wt%, alternatively from 1 wt% to 20.0 wt%, alternatively from 0.5 wt% to 15 wt%, as measured using the solubility test method.

An ASNM pre-catalyst may be a compound of formula (1) of FIG. 2, where M is a group 4 metalAnd each R is independently selected from the group consisting of silicon-containing organic solubilizing groups and non-silicon-containing organic solubilizing groups. By "solubilised" is meant that the R group confers what can be written as HN5MR₂Enhanced solubility of compound (1) of (1). In some aspects, at least one R is a silicon-containing organic solubilizing group, and the other R is a silicon-containing organic solubilizing group or a non-silicon-containing organic solubilizing group. In some aspects, each R is independently a silicon-containing organic solubilizing group. In some aspects, each R is independently an unsubstituted or substituted quaternary silicon hydrocarbyl group. Each quaternary silicon hydrocarbyl group containing one quaternary silicon atom and one (C)₁-C₃) Alkylene or (C)₇-C₈) Arylalkylene group, alternatively (C)₁-C₃) Alkylene, alternatively (C)₇-C₈) Arylalkylene group, alternatively one (C)₁-C₂) Alkylene groups. (C)₁-C₃) Alkylene or (C)₇-C₈) The arylalkylene group is located between the quaternary silicon atom and the metal M. Thus, the quaternary silicon atom passes through (C)₁-C₃) Alkylene or (C)₇-C₈) The arylalkylene group (e.g., benzylidene) is indirectly bonded to metal M, which in turn is directly bonded to metal M (e.g., M-CH)₂-phenylene-). A quaternary silicon atom is an element of atomic number 14 of the periodic Table of elements bonded to four carbon atoms, one of which is (C)₁-C₃) Alkylene or (C)₇-C₈) Carbon atom of arylalkylene group. In other aspects, each R is independently a silicon-free organic solubilizing group. In some aspects, each R group is unsubstituted.

Embodiment 3.ASNM precatalyst may be compound (1) of embodiment 2, wherein at least one, alternatively each R is independently of the formula- (C (R)^A)₂)_mQZR¹R²R³Wherein subscript m is 1,2, or 3; wherein each R^AIndependently is H or (C)₁-C₃) Alkyl, or each R^AWith R^A'-R^A' bonded together, wherein R^A'-R^A' is (C)₁-C₃) An alkylene group; each Q is independentDoes not exist in the field, (C)₁-C₃) Alkylene or unsubstituted or substituted phenylene; wherein each Z is independently C or Si; wherein each R¹、R²And R³Independently is independently unsubstituted or substituted by one or more substituents (C)₁-C₁₅) An alkyl group; and wherein each substituent is independently selected from unsubstituted (C)₁-C₅) Alkyl, halogen, -Oalkyl, -N (alkyl)₂and-Si (alkyl)₃. In certain aspects, provided that when subscript m is 2, the resulting (C (R)^A)₂)_mIs not C (R)^A)₂CH(R^A) Or C (R)^A)₂CH₂(ii) a And when the subscript m is 3, (C (R) is obtained^A)₂)_mIs not C (R)^A)₂CH(R^A)C(R^A)₂Or C (R)^A)₂CH₂C(R^A)₂. Optional conditions are intended to exclude compounds that may be susceptible to β -hydride elimination. In certain aspects, subscript m is 2, alternatively 1. In some aspects, each R^AIndependently H or unsubstituted (C)₁-C₄) Alkyl, alternatively H or methyl, alternatively H. In some aspects, each Q is absent. In some aspects, at least one, alternatively each Q is present. When present, each Q may independently be (C)₁-C₃) Alkylene, alternatively CH₂Alternatively CH₂CH₂Alternatively CH₂CH₂CH₂Alternatively CH₂CH(CH₃). Alternatively, each Q may independently be unsubstituted 1, 4-phenylene, unsubstituted 1, 3-phenylene, or unsubstituted 1, 2-phenylene; alternatively selected from any two of unsubstituted 1,4-, 1, 3-and 1, 2-phenylene; alternatively unsubstituted 1, 2-phenylene; alternatively unsubstituted 1, 3-phenylene; alternatively unsubstituted 1, 4-phenylene. 1, 2-phenylene is benzene-1, 2-diyl; the 1, 3-phenylene group is a benzene-1, 3-diyl group, and the 1, 4-phenylene group is a benzene-1, 4-diyl group. "unsubstituted phenylene" means having the formula C₆H₄A phenylene group of (1).

Embodiment 4 ASNM Pre-catalystA compound (1) which may be embodiment 2 or 3 wherein at least one, alternatively each R is independently-CH₂SiR¹R²R³(ii) a Wherein each R¹、R²And R³Independently is unsubstituted (C)₁-C₁₅) Alkyl, alternatively (C)₁-C₃) Alkyl, alternatively methyl. In some aspects, one R is-CH₂SiR¹R²R³And the other R is unsubstituted (C)₁-C₁₅) An alkyl group.

Embodiment 5.ASNM precatalyst may be compound (1) of embodiment 2,3 or 4, wherein at least one, alternatively each R is-CH₂- (unsubstituted phenylene) -ZR¹R²R³(ii) a Wherein each Z is Si or C; wherein each unsubstituted phenylene group is unsubstituted 1, 4-phenylene, unsubstituted 1, 3-phenylene, or unsubstituted 1, 2-phenylene; wherein each R¹、R²And R³Independently is unsubstituted (C)₁-C₁₅) Alkyl, alternatively (C)₁-C₃) Alkyl, alternatively methyl. In certain aspects, one R is-CH₂SiR¹R²R³And the other R is tert-butyl-phenylmethyl. At least one, alternatively each Z may be Si, alternatively C.

Embodiment 6.ASNM pre-catalyst may be compound (1) of embodiment 2, where each R is independently CH₂Si(CH₃)₃Or CH₂- (phenylene) -SiR¹R²R³(ii) a And wherein (i) R¹And R²Is methyl, and R³Is unsubstituted (C)₂-C₁₅) Alkyl, alternatively unsubstituted (C)₃-C₅) Alkyl, alternatively unsubstituted (C)₆-C₁₅) An alkyl group; or (ii) each R¹、R²And R³Is methyl.

Embodiment 7.ASNM pre-catalyst may be the compound (1) of embodiment 2, where one R is CH₂Si(CH₃)₃Or CH₂- (phenylene) -SiR¹R²R³(ii) a And wherein (i) R¹And R²Is methyl, and R³Is unsubstituted (C)₂-C₁₅) Alkyl, alternatively unsubstituted (C)₃-C₅) An alkyl group; or (ii) R¹、R²And R³Each is methyl; and wherein the other R is a quaternary alkyl substituted (C)₇-C₈) Arylalkyl radicals or unsubstituted (C)₁-C₁₅) An alkyl group. In some aspects, the quaternary alkyl substituted (C)₇-C₈) Arylalkyl is tert-butyl-phenylmethyl (i.e., 1, 1-dimethylethylphenylmethyl), alternatively CH₂- (1, 4-phenylene) -C (CH)₃)₃. In other aspects, another R is methyl, 2-dimethylpropyl, 2-dimethylhexyl or hexyl, 2-ethylhexyl.

An ASNM precatalyst may be a compound (1) of embodiment 6 or 7, wherein the phenylene group is (i) an unsubstituted 1, 4-phenylene group; (ii) unsubstituted 1, 3-phenylene; or (iii) unsubstituted 1, 2-phenylene. The phenylene group may be an unsubstituted 1, 4-phenylene group.

Embodiment 9.ASNM precatalyst may be compound (1) of any one of embodiments 2 to 8, wherein each R independently may be the same or different, and may be selected from: trimethylsilylmethyl, dimethylethylsilylmethyl, dimethyl (n-propyl) silylmethyl, dimethyl (n-butyl) silylmethyl, dimethyl (n-pentyl) silylmethyl, dimethyl (n-hexyl) silylmethyl, dimethyl (n-heptyl) silylmethyl, dimethyl (n-octyl) silylmethyl, dimethyl (n-decyl) silylmethyl, dimethyl (n-dodecyl) silylmethyl, triethylsilylmethyl, methyldiethylsilylmethyl, dimethyl (2-ethylhexyl) silylmethyl, dimethyl (trimethylsilylmethyl) silylmethyl, dimethyl (3, 3-dimethylbutyl) silylmethyl, dimethyl (1, 1-dimethylethyl) silylmethyl and dimethyl (2-methylpropyl) silylmethyl.

Embodiment 10.ASNM precatalyst is compound (1A) of figure 2.

Embodiment 11. aspects wherein each R is independently a silicon-free organic solubilizing group. The ASNM precatalyst may be compound (1) of embodiment 2, wherein each R is independently methyl, unsubstituted (C)₂-C₄) Alkyl radical, unsubstituted (C)₅-C₁₂) Alkyl groups (e.g. unsubstituted (C)₅-C₉) Alkyl radicals or unsubstituted (C)₁₀-C₁₂) Alkyl groups), unsubstituted or substituted quaternary arylalkyl groups; or two R groups are bonded together to give R '-R', wherein R '-R' is unsubstituted or substituted (aryl) alkylene. Each of the R groups and R '-R' groups of embodiment 11 is free of cyclopentadienyl groups, silicon atoms, carbon-carbon double bonds, and carbon-carbon triple bonds. Each substituent may be independently selected from unsubstituted (C)₁-C₅) Alkyl, halogen, -Oalkyl and-N (alkyl)₂. Each quaternary arylalkyl group comprises, in order, (C) a quaternary alkyl group, a phenylene group, and₁-C₃) An alkylene linker. The quaternary alkyl group being bonded to the phenylene group bonded to (C)₁-C₃) An alkylene group, the latter bonded to the metal M. (C)₁-C₃) The alkylene linking group and the R '-R' group are divalent. The quaternary alkyl group contains a quaternary carbon atom that can be bonded directly or indirectly to the phenylene group. A quaternary carbon atom is an element of atomic number 6 of the periodic table of elements bonded to four other carbon atoms.

Embodiment 12.ASNM precatalyst may be a compound (1) of embodiment 11, wherein each R is independently methyl, unsubstituted (C)₂-C₄) Alkyl radicals or unsubstituted (C)₅-C₁₂) Alkyl groups (e.g. unsubstituted (C)₅-C₉) An alkyl group). In some aspects, each R is methyl, alternatively each R is unsubstituted (C)₂-C₄) Alkyl groups, alternatively each R is unsubstituted (C)₅-C₉) Alkyl groups, alternatively one R is methyl and the other R is unsubstituted (C)₅-C₉) An alkyl group. In some aspects unsubstituted (C)₅-C₉) The alkyl group is 2, 2-dimethylpropyl (neopentyl).

Embodiment 13.ASNM precatalyst may be a compound (1) of embodiment 11, wherein two R groups are bonded together to give R '-R', wherein R '-R' is unsubstituted or substituted alkylene, alternatively substituted (C)₄-C₅) An alkylene group. In some aspects, R '-R' is- (CH)₂)₃C(H)(R⁴)CH₂-or-CH₂(C(R⁴)))₂CH₂-, wherein each R⁴Independently is unsubstituted (C)₁-C₅) An alkyl group. R '-R' can be 2,2,3, 3-tetramethylbutane-1, 4-diyl or 2- (2',2' -dimethylpropyl) -pentane-1, 5-diyl.

Embodiment 14.ASNM precatalyst may be a compound (1) of embodiment 11, where two R groups are bonded together to give R '-R', where R '-R' is a substituted arylalkylene group, alternatively 4- (unsubstituted (C)₁-C₅) Alkyl) -1, 2-xylylene. 4- (unsubstituted (C)₁-C₅) Alkyl) -1, 2-xylylene is-CH₂- [4- (unsubstituted (C)₁-C₅) Alkyl- (1, 2-phenylene)]-CH₂-. In some aspects, 4- (unsubstituted (C)₁-C₅) Alkyl) -1, 2-xylylene is 4- (2, 2-dimethylpropyl) -1, 2-xylylene (i.e., -CH)₂-[4-(CH₃C(CH₃)₂CH₂) - (1, 2-phenylene)]-CH₂-)。

Embodiment 15.ASNM precatalyst may be compound (1) of any one of embodiments 11 to 14, wherein each R is the same or different and is independently selected from: methyl, 2-dimethylpropyl, 2-dimethylhexyl, 2-dimethyloctyl, 2-ethylhexyl, 2-ethyloctyl, 2-tert-butylphenyl-methyl, 3-tert-butylphenyl-methyl, 4-tert-butylphenyl-methyl, 2-ethylphenyl-methyl, 3-n-butylphenyl-methyl, 4-n-butylphenyl-methyl, 2-n-butylphenyl-methyl, 3-ethylphenyl-methyl, 4-ethylphenyl-methyl, 2-n-octylphenyl-methyl, 3-n-octylphenyl-methyl and 4-n-octylphenyl-methyl. In certain aspects, each R is the same.

Embodiment 16.ASNM precatalyst is compound (1B), (1C), (1D) or (1E) of figure 2. In certain aspects, compound (1) is any one of compounds (1A) to (1E), alternatively compound (1) is selected from any four of compounds (1A) to (1E); alternatively compound (1) is compound (1B) or (1C); alternatively compound (1) is compound (1D) or (1E); alternatively compound (1) is compound (1A); alternatively compound (1) is compound (1B); alternatively compound (1) is compound (1C); alternatively compound (1) is compound (1D); alternatively compound (1) is compound (1E).

An ASNM precatalyst may be a compound (1) of any one of embodiments 2 to 16, wherein M is Zr. In other aspects, M is Hf.

Embodiment 18. the ASNM precatalyst of any of embodiments 1 to 17, characterized by the inclusion of at least 60 wt.% n-hexane (CH)₃(CH₂)₄CH₃) Has a solubility in hexane of 0.50 to 24 wt%.

Synthesis of Compound (1)

The compound of formula (1) can be prepared by reacting a compound of formula (2) of FIG. 3 with a compound of formula X¹MgR or M¹Rn, wherein M is as defined for compound (1), and each X is independently Cl, Br or I; wherein R is as defined for compound (1) according to any one of the preceding aspects; x¹Is Cl, Br or I; m¹Selected from Li, Zn, Sn and Cu; and subscript n is an integer of 1 to 4 and is equal to M¹Formal oxidation state of (a); under effective reaction conditions in an aprotic solvent, thereby synthesizing a compound of formula (1). The molar ratio of compound (2) to organometallic halide reagent may be 1:2 to 1: 10.

The synthesis of compound (1) may also comprise reacting a compound of formula (3) of FIG. 3 with a compound of formula X-Si (CH)₃)₃The preliminary step of contacting the reagent of (1), wherein each R¹⁰Independently is (C)₁-C₁₅) Alkyl, alternatively (C)₁-C₆) Alkyl, wherein X is as defined for compound (2), in an aprotic solvent under effective reaction conditions.

The synthesis of compound (1) may further comprise reacting a compound of formula (4) of FIG. 3 with a compound of formula M (N (R)¹⁰)₂)₄Wherein M is as defined for compound (1), and each R is¹⁰Independently is (C)₁-C₁₅) Alkyl, in an aprotic solvent under effective reaction conditions to synthesize the compound (3). Each R¹⁰May independently be (C)₁-C₆) Alkyl, alternatively methyl or ethyl. Compound (4) with M (N (R)¹⁰)₂)₄May be in the range of 1:10 to 10: 1.

The aprotic solvent can independently be a hydrocarbon solvent, such as an alkyl aromatic hydrocarbon (e.g., toluene, xylene), an alkane, a chlorinated aromatic hydrocarbon (e.g., chlorobenzene), a chlorinated alkane (e.g., dichloromethane), a dialkyl ether (e.g., diethyl ether), or a mixture of any two or more thereof.

The synthesis can be carried out under effective reaction conditions. Effective reaction conditions may include techniques for manipulating air-sensitive and/or moisture-sensitive reagents and reactants, such as schlenk line techniques and inert gas atmospheres (e.g., nitrogen, helium, or argon). Effective reaction conditions may also include sufficient reaction time, sufficient reaction temperature, and sufficient reaction pressure. Each reaction temperature may independently be-78 ℃ to 120 ℃, alternatively-30 ℃ to 30 ℃. Each reaction pressure may independently be 95kPa to 105kPa, alternatively 99kPa to 103 kPa. The progress of any particular reaction step can be monitored by analytical methods such as Nuclear Magnetic Resonance (NMR) spectroscopy or mass spectrometry. The reaction time may independently be 30 minutes to 48 hours.

Compound (1) solves the instability problem of existing alkane insoluble non-MCN precatalysts, since compound (1) can be stored in solution in an alkane without activator.

Embodiments of the trimmed catalyst made from compound (1) and activator have faster light-off than a comparative catalyst system made from HN5Zr dibenzyl and the same activator. And compound (1) can produce a polyethylene having the same MWD as the MWD of the polyethylene produced from the comparative catalyst system. Faster light-off of the trimmed catalyst system prepared from compound (1) and activator can advantageously result in reduced distributor plate fouling in a gas phase polymerization reactor containing a recycle loop, whereby some polymer particles with active catalyst are entrained back into the reactor where they can grow and foul the distributor plate. The faster light-off of the trimmed catalyst may be characterized by a shorter time to reach the highest temperature measured in vitro using 1-octene as a monomer according to the light-off test method described later.

Tailoring the catalyst (e.g., prepared from compound (1) and an activator) enables the preparation of polyethylene resins having a smaller proportion of particles characterized as "fines", which will be defined later. There are many well-known reasons why fines may be operating a gas-phase polymerization reactor (such as UNIPOL from united Technologies, LLC) with a recycle line and/or an enlarged upper section^TMReactor or other reactor) causes problems. Fines are known to contribute to an increased tendency to static electricity and film formation in such reactors. Fines can increase the retention of particles from the reactor to the recycle line and cause fouling of the interior of the recycle loop, such as in the heat exchanger, compressor, and/or distributor plate. Fines can also accumulate in the enlarged portion of the reactor, as it is believed that fines are more prone and/or susceptible to electrostatic forces. Fines can also cause problems for polyethylene polymers produced by gas phase polymerization in such reactors. The fines can continue to polymerize in the cold zone of the reactor (in the recycle loop or in the expanded section) and produce polyethylene having a molecular weight higher than the target molecular weight in the bulk fluidized bed. Fines may eventually return from the recycle loop to the fluidized bed and then into the polyethylene product, resulting in a higher gel content in the polyethylene product. Polyethylene resins produced from a trim catalyst made from compound (1) and an activator have reduced weight% fines.

Tailoring the catalyst (e.g., prepared from compound (1) and an activator) enables the preparation of polyethylene resins having larger particle sizes than polyethylene resins prepared from a comparative catalyst system (prepared from HN5Zr dibenzyl and the same activator). The larger particle size polyethylene resins prepared by the catalyst system of the present invention can be used to reduce the settled bulk density of the resin. Resins with higher proportions of fines can have higher settled bulk density because smaller particles of fines can move down and fill the spaces between larger particles. If the settled bulk density is too high, the resin may be difficult to fluidize, leading to local overheating and formation of resin lumps in certain areas of the reactor process, such as near the edges of the distributor plate or in the product discharge system.

A polyethylene resin can be made using a bimodal catalyst system in which an alkane solution of the (first or second) ASNM catalyst is used as the trim catalyst (second part) and a combination of all MCN pre-catalyst, activator and the remainder of the (first or second) ASNM catalyst is used as the first part, all part mixed feed processes can reduce gel content compared to a polyethylene resin made using the same bimodal catalyst system, except where supported HN5Zr dibenzyl is used as the trim catalyst and the remainder of HN5Zr dibenzyl and the same MCN pre-catalyst are used as the first part. Since the solubility of the (first or second) ASNM catalyst in hexane containing at least 60 wt% n-hexane is significantly greater than that of HN5Zr dibenzyl, the (first or second) ASNM catalyst can be fed as an alkane solution (e.g., typically a solution in mineral oil) as a trim catalyst in the "fractional mix" feed process described previously, whereby it can be mixed with a bimodal catalyst system in an in-line mixer, resulting in a trimmed bimodal catalyst system that can produce a bimodal polyethylene composition without the increased gel content found for HN5Zr dibenzyl for the reasons described above, and addresses the earlier gel problem.

The hydrocarbon solvent is a liquid material at 25 ℃, which consists of carbon and hydrogen atoms and optionally one or more halogen atoms, and is free of carbon-carbon double bonds and carbon-carbon triple bonds. The hydrocarbon solvent may be an alkane, aromatic (toluene) or alkylaromatic (i.e., arylalkane, xylene). Examples of hydrocarbon solvents are alkanes such as mineral oil, Isopar-C, Isopar-E, and mineral oils such as white mineral oil, pentane, hexane (e.g., hexane containing at least 60 wt% n-hexane), heptane, octane, nonane, decane, undecane, dodecane, hexane, 1-methylpentane (isohexane), heptane, 1-methylhexane (isoheptane), octane, nonane, decane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, methylcyclopentane, methylcyclohexane, dimethylcyclopentane, or mixtures of any two or more thereof. Or the process may be mineral oil free.

Hexane comprising at least 60% by weight of n-hexane is a mixture of alkanes consisting essentially of from 60% to 70% by weight of n-hexane, from 40% to 10% by weight of one or more compounds of formula C other than n-hexane₆H₁₄Compound and 0 to 30 wt% of methylcyclopentane. In some aspects, the alkane mixture consists essentially of 60 wt% to 70 wt% n-hexane, 40 wt% to 30 wt% of one or more compounds of formula C other than n-hexane₆H₁₄The compound consists of and does not contain methylcyclopentane. In other aspects, the alkane mixture consists essentially of from 60 wt% to 70 wt% n-hexane, less than 40 wt% to 10 wt% of one or more compounds of formula C other than n-hexane₆H₁₄A compound and greater than 0 wt% to 30 wt% methylcyclopentane (e.g., 20 wt% to 30 wt% methylcyclopentane). Formula C other than n-hexane₆H₁₄Examples of compounds are 2-methylpentane, 3-methylpentane and mixtures thereof. The phrase "consisting essentially of means free of solvents other than the aforementioned alkanes. Hexanes comprising at least 60% by weight n-hexane can be anhydrous and/or insoluble in molecular oxygen.

The metallocene precatalyst may be any of the metallocene catalyst components described in US7873112B2 column 11 line 17 to column 22 line 21. In certain aspects, the metallocene precatalyst is selected from the metallocene precatalyst materials named in US7873112B2 column 18 line 51 to column 22 line 5. In certain aspects, the metallocene precatalyst is selected from the group consisting of bis (. eta.5-tetramethylcyclopentadienyl) zirconium dichloride, bis (. eta.5-tetramethylcyclopentadienyl) zirconium dimethyl, bis (. eta.5-pentamethylcyclopentadienyl) zirconium dichloride, bis (. eta.5-pentamethylcyclopentadienyl) zirconium dimethyl, (1, 3-dimethyl-4, 5,6, 7-tetrahydroindenyl) (1-methylcyclopentadienyl) zirconium dimethyl, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dimethyl, bis (n-propylcyclopentadienyl) hafnium dichloride, bis (n-propylcyclopentadienyl) hafnium dimethyl; bis (n-butylcyclopentadienyl) zirconium dichloride and bis (n-butylcyclopentadienyl) zirconium dimethyl. In some aspects, the metallocene catalyst is the product of an activation reaction of an activator and any of the above metallocene precatalysts.

ASNM and MCN catalysts can be prepared under effective activation conditions. Effective activation conditions may include techniques for manipulating the catalyst, such as in-line mixers, catalyst preparation reactors, and polymerization reactors. Activation may be performed in an inert gas atmosphere (e.g., nitrogen, helium, or argon). Effective activation conditions may also include a sufficient activation time and a sufficient activation temperature. Each activation temperature may independently be 20 ℃ to 800 ℃, alternatively 300 ℃ to 650 ℃. The activation time may be 10 seconds to 2 hours.

An activator, also referred to as a cocatalyst, is a compound or composition comprising a combination of reagents, wherein the compound or composition increases the rate at which a transition metal compound (e.g., compound (1) or metallocene precatalyst) oligomerizes or polymerizes an unsaturated monomer, such as an olefin, such as ethylene or 1-octene. The activator may also affect the molecular weight, branching, comonomer content, or other properties of the oligomer or polymer (e.g., polyolefin). The transition metal compound (e.g., compound (1) or metallocene precatalyst) may be activated for oligomerization and/or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and/or polymerization. Typically, the activator comprises aluminum and/or boron, alternatively aluminum. Examples of suitable activators are alkylalumoxanes and trialkylaluminum compounds.

Alumoxane (alumoxane) activators may be used as activators for one or more pre-catalyst compositions comprising compound (1) or metallocene pre-catalyst. Aluminoxanes are generally oligomeric compounds comprising-Al (R) -O-subunits, where R is an alkyl group; they are known as alkylaluminoxanes (alkylaluminoxanes). The alkylalumoxanes can be unmodified or modified. Examples of alkylaluminoxanes include Methylaluminoxane (MAO), Modified Methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Unmodified alkylaluminoxanes and modified alkylaluminoxanes are suitable as activators for precatalysts such as compound (1). Mixtures of different aluminoxanes and/or different modified aluminoxanes may also be used. For further description, see U.S. Pat. nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, and EP 0561476, EP 0279586, EP 0516476, EP 0594218, and PCT publication WO 94/10180.

When the activator is an alumoxane (modified or unmodified), the maximum amount of activator can be selected to be a 5,000 times molar excess of the precursor based on the molar ratio of the moles of Al metal atoms in the alumoxane to the moles of metal atoms M (e.g., Zr or Hf) in the precatalyst (e.g., compound (1)). Alternatively or additionally, the minimum amount of activator to precatalyst precursor may be in a 1:1 molar ratio (Al/M).

The trialkylaluminum compound may be used as an activator for a precatalyst (e.g., compound (1) or metallocene precatalyst) or as a scavenger to remove residual water therefrom prior to the start-up of the polymerization reactor. Examples of suitable alkylaluminum compounds are trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum.

The support material is a particulate solid, which may be non-porous, semi-porous or porous. The support material is a porous support material. Examples of support materials are talc, inorganic oxides, inorganic chlorides, zeolites, clays, resins and mixtures of any two or more thereof. Examples of suitable resins are polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins.

The inorganic oxide support material comprises a group 2,3,4,5, 13 or 14 metal oxide. Preferred supports include silica, fumed silica, alumina (see, e.g., PCT publication WO99/60033), silica-alumina, and mixtures thereof, which may or may not be dehydrated. Other useful supports include magnesia, titania, zirconia, magnesium chloride (U.S. Pat. No. 5,965,477), montmorillonite (EP 0511665), phyllosilicates, zeolites, talc, clays (U.S. Pat. No. 6,034,187), and the like. Also, combinations of these support materials may be used, such as silica-chromium, silica-alumina, silica-titania, and the like. Additional support materials may include those porous acrylic polymers described in EP 0767184, which is incorporated herein by reference. Other support materials include nanocomposites as disclosed in PCT publication WO 99/47598, aerogels as disclosed in PCT publication WO 99/48605, pellets as disclosed in U.S. patent No. 5,972,510, and polymer beads as disclosed in PCT publication WO 99/50311.

The support material may have a range of about 10m²G to about 700m²Surface area per gram, in the range of about 0.1cm³G to about 4.0cm³Pore volume per gram and average particle size in the range of about 5 microns to about 500 microns. The support material may be silica (e.g., fumed silica), alumina, clay or talc. Fumed silica can be hydrophilic (untreated), alternatively hydrophobic (treated). In some aspects, the support is a hydrophobic fumed silica, which can be prepared by treating an untreated fumed silica with a hydrophobic agent such as dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane. In some aspects, the treating agent is dimethyldichlorosilane. In one embodiment, the carrier is Cabosil^TMTS-610。

The one or more precatalysts and/or one or more activators may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in or on one or more supports or carrier materials.

The metallocene precatalyst may be spray dried according to the general method described in US 5648310. The support used with compound (1) and any other precatalyst may be functionalized as generally described in EP 0802203, or at least one substituent or leaving group selected as described in US 5688880.

Polymerization reactor and process

Solution phase and/or slurry phase polymerization of olefin monomers is well known. See, for example, US8291115B 2.

Gas Phase Polymerization (GPP) is well known. The polymerization uses GPP reactors, such as stirred bed gas phase polymerization reactors (SB-GPP reactors) or fluidized bed gas phase polymerization reactors (FB-GPP reactors). Such reactors and processes are generally well known. For example, the FB-GPP reactor/process may be as described in any of US 3,709,853, US 4,003,712, US 4,011,382, US 4,302,566, US 4,543,399, US 4,882,400, US5,352,749, US5,541,270, US 2018/0079836 ｃA1, EP- ｃA-0802202, and belgium patent No. 839,380. These SB-GPP and FB-GPP polymerization reactors and processes mechanically agitate or fluidize the polymerization medium inside the reactor by continuous flow of gaseous monomer and diluent, respectively. Other useful reactors/processes contemplated include serial or multistage polymerization processes such as those described in U.S. Pat. No. 5,627,242, U.S. Pat. No. 5,665,818, U.S. Pat. No. 5,677,375, EP-A-0794200, EP-B1-0649992, EP-A-0802202 and EP-B-634421.

The gas phase polymerization operating conditions are any variable or combination of variables that may affect the polymerization reaction in the GPP reactor or the composition or properties of the polyolefin polymer composition product produced therefrom. Variables may include reactor design and size, pre-catalyst composition and amount, reactant composition and amount, molar ratio of two different reactants, feed gas such as H₂Presence or absence of (a), molar ratio of feed gas to reactant(s), interfering material (e.g., H)₂O and/or O₂) The absence or concentration of Induced Condensing Agent (ICA), the absence or presence of Induced Condensing Agent (ICA), the average polymer residence time in the reactor, the partial pressure of the ingredients, the feed rate of the monomers, the reactor bed temperature (e.g., fluidized bed temperature), the nature or sequence of the process steps, the transition period between steps. Variables other than the variable/variables described or changed by the method or use may be held constant.

Ethylene control ("C") in GPP Processes₂"), hydrogen gas (" H ")₂") and 1-hexene (" C₆"or" C_x", where x is 6) of the individual flow ratesTo maintain a fixed comonomer to ethylene monomer gas mole ratio (C) equal to the values described (e.g., 0.00560 or 0.00703)_x/C₂E.g. C₆/C₂) Constant hydrogen to ethylene gas molar ratio ("H") equal to the value described (e.g., 0.00229 or 0.00280)₂/C₂") and constant ethylene (" C ") equal to the value described (e.g., 1,000kPa)₂") partial pressure. The gas concentration was measured by on-line gas chromatography to understand and maintain the composition in the recycle gas stream. The reacting bed of growing polymer particles is maintained in a fluidized state by continuously flowing the make-up feed and recycle gas through the reaction zone. Superficial gas velocities of 0.49 to 0.67 meters per second (1.6 to 2.2 feet per second (ft/s)) were used. The FB-GPP reactor is operated at a total pressure of about 2344 kilopascals (kPa) to about 2413 kilopascals (about 340 psig to about 350 psig) and at the first reactor bed temperature RBT as described. The fluidized bed is maintained at a constant height by withdrawing a portion of the bed at a rate equal to the production rate of the polyolefin polymer composition in particulate form, which can range from 10 kilograms per hour (kg/h) to 20 kilograms per hour. Semi-continuously moving the product polyolefin polymer composition into a fixed volume chamber via a series of valves, wherein the removed bimodal ethylene-co-1-hexene copolymer composition is purged to remove entrained hydrocarbons and subjected to humid nitrogen (N)₂) The gas stream is treated to deactivate any traces of residual catalyst.

The catalyst system may be fed to the polymerization reactor in "dry mode" or "wet mode", alternatively dry mode, alternatively wet mode. The dry mode is a dry powder or granules. The wet mode is a suspension in an inert liquid such as mineral oil.

Induced Condensing Agent (ICA). An inert liquid can be used to cool materials in a GPP reactor. Its use is optional. ICA may be (C)₅-C₂₀) Alkanes, such as 2-methylbutane (i.e., isopentane). See US 4,453,399, US 4,588,790, US 4,994,534, US5,352,749, US5,462,999 and US6,489,408. The ICA concentration in the reactor may be 1 mol% to 10 mol%。

GPP conditions may also include one or more additives, such as chain transfer agents or accelerators. Chain transfer agents are well known and may be metal alkyls, such as diethyl zinc. Promoters are known such as in US 4,988,783, and may include chloroform, CFCl₃Trichloroethane and difluorotetrachloroethane. The scavenger may be used to react with moisture prior to reactor startup and may be used to react with excess activator during reactor changeover. The scavenger may be a trialkylaluminium. GPP can operate without (unintentionally added) scavenger. The GPP reactor/process can also include an amount (e.g., 0.5ppm to 200ppm based on all feeds to the reactor) of static control agents and/or continuity additives, such as aluminum stearate or polyethyleneimine. Static control agents may be added to the FB-GPP reactor to inhibit the formation or accumulation of static charge therein.

The GPP reactor can be a commercial scale FB-GPP reactor, such as UNIPOL available from Univation Technologies, LLC, a subsidiary of The Dow Chemical Company, Midland, Michigan, USA of Midland, Mich^TMReactor or UNIPOL^TMII, a reactor.

Any compound, composition, formulation, material, mixture, or reaction product herein may be free of any of the chemical elements selected from the group consisting of: H. li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, lanthanides and actinides; provided that the chemical elements required for the compound, composition, formulation, material, mixture, or reaction product (e.g., Zr required for a zirconium compound, or C and H required for polyethylene, or C, H and O required for an alcohol) are not counted.

Definition of

Alkane (solvent). A orMultiple formula C_nH_2n+2And/or one or more acyclic compounds of formula C_mH_2mWherein subscripts n and m are independently integers of from 5 to 50 (e.g., 6).

Bimodal. There are (only) two maxima in the frequency distribution. As bimodal polymer composition or bimodal catalyst system. The bimodal catalyst system comprises two different catalysts and produces a bimodal polymer composition consisting essentially of a Higher Molecular Weight (HMW) component and a Lower Molecular Weight (LMW) component. Bimodal polymer compositions include a post-reactor blend (the LMW component and the HMW component are synthesized separately in different reactors or at different times in the same reactor and then blended together, such as by melt extrusion) and a reactor blend (the LMW component and the HMW component are synthesized in the same reactor). Bimodal copolymer compositions can be characterized by a plot of dW/dlog (mw) on the y-axis versus log (mw) on the x-axis, the two peaks separated by a distinguishable local minimum, giving a Gel Permeation Chromatography (GPC) plot, wherein log (mw) and dW/dlog (mw) are as defined herein and measured by the GPC testing methods described herein.

And (5) drying. Generally, the moisture content is from 0 parts per million to less than 5 parts per million based on the total weight parts. The material fed to the reactor during the polymerization reaction is dry.

A Higher Molecular Weight (HMW) component. Macromolecular subgroups with peaks of higher molecular weight in the GPC plots of dW/dLog (MW) on the y-axis versus Log (MW) on the x-axis.

A hydrocarbyl group. A monovalent group formally obtained by removing a hydrogen atom from a hydrocarbon compound composed of C and H atoms.

Alkylene groups. A divalent group formally obtained by removing two H atoms from a hydrocarbon compound consisting of C and H atoms, wherein the two H atoms are removed from different carbon atoms of the hydrocarbon compound.

And (4) inertia. In general, it is not (significantly) reactive or interferes with the polymerization reaction of the present invention. Applied to purge gas or ethylene feedThe term "inert" means molecular oxygen (O) based on the total parts by weight of the purge gas or ethylene feed₂) The content is 0 to less than 5 parts per million.

A Lower Molecular Weight (LMW) component. Macromolecular subgroups with peaks of lower molecular weight in the GPC plots of dW/dLog (MW) on the y-axis versus Log (MW) on the x-axis.

A metallocene catalyst. Homogeneous or heterogeneous materials comprising a (substituted or unsubstituted) -cyclopentadienyl ligand-metal complex and enhancing the rate of olefin polymerization. Essentially single or double sites. Each metal is a transition metal Ti, Zr or Hf.

Multimodal. With two or more maxima in the frequency distribution.

Ziegler-Natta catalysts (Ziegler-Natta catalysts). Heterogeneous materials that enhance the olefin polymerization rate and are prepared by contacting an inorganic titanium compound, such as a titanium halide, supported on a magnesium chloride support with an activator.

Alternatively before the different embodiments. ASTM is the Standard organization, ASTM International (ASTM International, West Consho-hocken, Pennsylvania, USA) of West Conshoken, West, Inc. Any comparative examples are used for illustrative purposes only and should not be prior art. Absent or not means completely absent; alternatively not detectable. Unless otherwise defined, terms used herein have their IUPAC meanings. See, for example, the general catalog of Chemical nomenclature (Compendium of Chemical technology). Golden book, version 2.3.3, 24 months 2 2014. IUPAC is the International Union of Pure and Applied Chemistry (International Union of Pure and Applied Chemistry) (the IUPAC secretary of Triangle Research Park, N.C.A., USA (IUPAC Secretariat, Research Triangle Park, North Carolina, USA)). The periodic table of elements is the IUPAC version released 5 months and 1 days in 2018. The option may be given, rather than being indispensable. Operability means functionally capable or effective. Optional (optionally) means absent (or excluded), alternatively present (or included). The properties can be measured using standard test methods and conditions. Ranges include endpoints, subranges, and integer and/or fractional values subsumed therein, except that integer ranges do not include fractional values. Room temperature: 23 ℃. + -. 1 ℃ "HN 5" was not pentoxazole.

Examples

Isoparaffinic fluids: ISOPAR-C available from ExxonMobil, ExxonMobil.

Mineral oil: HYDROBRITE 380PO white mineral oil available from einthomson corporation (Sonneborn).

Preparation example 1A: preparation of an activator formulation comprising spray dried methylalumoxane/treated fumed silica (sdMAO) in hexane/mineral oil. 1.6kg of treated fumed silica (CAPOSIL TS-610) in 16.8kg of toluene was slurried, followed by the addition of 10 wt% (11.6kg) MAO in toluene to give a mixture. Using a spray dryer set at 160 ℃ and an outlet temperature of 70 ℃ to 80 ℃, the mixture was introduced into the atomization device of the spray dryer to produce droplets of the mixture, which were then contacted with a stream of hot nitrogen gas to evaporate liquid from the mixture to give a powder. The powder was separated from the gas mixture in a cyclone and then discharged into a vessel to obtain sdMAO as a fine powder.

Preparation example 1B: preparation of a slurry of the activator formulation of preparation 1A. The sdMAO powder of preparation 1A in a mixture of 10 wt% n-hexane and 78 wt% mineral oil was slurried to give an activator formulation with 12 wt% sdMAO in hexane/mineral oil/treated fumed silica solid.

Preparation example 2: preparation of spray-dried metallocene with activator formulation. Preparation examples 1A and 1B were repeated except that 1.5kg of treated fumed silica (CAPOSIL TS-610) in 16.8kg of toluene was slurried and then 10 wt% (11.1kg) MAO in toluene and a sufficient amount of (MeCp) (1, 3-dimethyl-4, 5,6, 7-tetrahydroindenyl) ZrMe was added₂Where Me is methyl, Cp is cyclopentadienyl, and MeCp is methylcyclopentadienyl, giving a loading of 40 micromoles Zr per gram of solid, to prepare an activator formulation. The resulting powder was slurried to give a 22 wt% solids activator formulation in 10 wt% isoparaffinic fluid and 68 wt% mineral oil. Advantageously, the activator formulation does notComprises a HMW pre-catalyst and can be used to produce polymer compositions having a very low HMW/LMW component ratio. Furthermore, the transition to other catalyst systems is simplified compared to the split mixed feed process in the preamble.

Preparation example 3: synthesis of Compound (4) { (HN (CH2CH2NHC6(CH3)5)2) }. Step 2 of US6967184B2, column 33, line 53 to column 34, line 9, was repeated to give compound (4), as described above.

Preparation example 4: 4-tert-butyl benzyl magnesium chloride. The first oven-dried 120mL glass jar was charged with three small PTFE-coated magnetic stir bars and 1.33g (54.7mmol) of magnesium turnings in a glove box with freezer parts under a nitrogen atmosphere. The jar was sealed with a PTFE-lined lid and the contents were vigorously stirred for 40 hours. PTFE is poly (tetrafluoroethylene). 40mL of anhydrous degassed ether was then added. The jar was placed in a glove box freezer for 15 minutes to cool the contents of the jar to-30 ℃. In a second oven dried 120mL glass jar, a solution of 4- (1,1, -dimethylethyl) benzyl chloride solution (2.0g, 10.9mmol) in 60mL anhydrous degassed ether was prepared. The jar was sealed with a PTFE-lined lid and then a second glass jar was placed in a glove box freezer for 15 minutes to cool its contents to-30 ℃. The solution of the second jar was added to the addition funnel and the contents of the addition funnel were then added dropwise to the contents of the first glass jar over 45 minutes. The residual contents of the addition funnel were rinsed into the reaction mixture of the first glass jar using 10mL of diethyl ether. The resulting mixture was stirred and allowed to reach room temperature for 2.5 hours. The mixture was filtered through a PTFE frit into a clean vial to give a solution of 4-tert-butylbenzylmagnesium chloride in diethyl ether. A portion of the filtrate was titrated with iodine/LiCl to determine the concentration of 4-tert-butylbenzylmagnesium chloride in solution.

Preparation example 5: and (3) synthesizing 3-n-butyl benzyl alcohol. In a glove box under nitrogen atmosphere, an oven-dried round bottom flask was charged with a PTFE-coated magnetic stir bar and a reflux condenser was charged with 3-n-butylbenzoic acid (2.0g, 11.2mmol) and 10mL dry degassed THF. Adding boronA tetrahydrofuran solution of an alkane (22.4mL, 22.4mmol), a reflux condenser was attached to the flask, and the mixture was heated to reflux for 4 hours. The flask was removed from the glove box and placed on a schlenk line under a nitrogen atmosphere and then cooled to 0 ℃ in an ice bath. 5mL of ethanol was added slowly, and the resulting mixture was poured into 30mL of water and extracted with three 30mL portions of diethyl ether. The ether extracts were combined and dried over anhydrous magnesium sulfate, filtered through celite, and concentrated under reduced pressure to give a light orange oil. The oil was dissolved in a minimal amount of hexane, and the solution was passed through a plug of silica gel, eluting with a 1:1 volume/volume (v/v) mixture of ethyl acetate and hexane. The filtrate was concentrated under reduced pressure to give 3-n-butylbenzyl alcohol as a pale orange oil.¹H NMR (400MHz, chloroform-d) δ 7.28-7.23 (m,1H), 7.19-7.14 (m,3H),7.10(dd, J ═ 7.5,1.5Hz,1H),4.65(s,2H), 2.63-2.55 (m,2H),1.64(d, J ═ 11.9Hz,2H), 1.64-1.54 (m,2H), 1.41-1.28 (m,2H),0.91(t, J ═ 7.3Hz, 4H).¹³C NMR (101MHz, chloroform-d) delta 143.31,140.76,128.44,127.77,127.08,124.26,65.49,35.60,33.63,22.38, 13.94.

Preparation example 6: 3-n-butylbenzyl chloride synthesis. A100 mL round bottom flask was charged with n-butylbenzyl alcohol (1.57g, 9.6mmol) prepared in preparation example 5 under nitrogen on a Schlenk line, and then 12mL of dry degassed dichloromethane was added. The flask was cooled to 0 ℃ in an ice bath and 0.1mL of triethylamine (0.8mmol) and thionyl chloride (1.39mL, 19.1mmol) were added slowly via syringe. The mixture was stirred under a nitrogen atmosphere and allowed to warm to room temperature over 22 hours. The mixture was carefully poured into 50mL of ice-water and extracted with three portions of 30mL of dichloromethane. The combined dichloromethane layers were washed with two 50mL portions of saturated aqueous sodium bicarbonate and two 50mL portions of saturated aqueous sodium chloride, then dried over magnesium sulfate and concentrated under reduced pressure. 3-n-butylbenzyl chloride was obtained as a pale yellow liquid.¹H NMR (400MHz, chloroform-d) δ 7.25(dd, J ═ 8.3,7.4Hz,1H), 7.21-7.16 (m,2H),7.12(dt, J ═ 7.4,1.6Hz,1H),4.56(s,2H), 2.64-2.56 (m,2H), 1.65-1.50 (m,3H),1.34(dq, J ═ 14.6,7.3Hz,2H),0.92(t, J ═ 7.3Hz, 3H).¹³C NMR (101MHz, chloroform-d) delta 143.51,137.32,128.63,128.59,128.51,125.83,46.43,35.50,33.53,22.37,13.93。

preparation example 7: and (3) synthesizing 3-n-butylbenzylmagnesium chloride. A first oven-dried 40mL glass vial was charged with three small PTFE-coated magnetic stir bars and 330mg (13.7mmol) of magnesium turnings in a glove box with freezer parts under a nitrogen atmosphere. The vial was sealed with a PTFE-lined septum cap and the contents were vigorously stirred for 40 hours. 10mL of anhydrous degassed ether was then added. The jar was placed in a glove box freezer for 15 minutes to cool the contents of the jar to-30 ℃. In a second oven dried 40mL glass vial, a solution of the 3-n-butylbenzyl chloride solution of preparation 6 (0.5g, 10.9mmol) in 15mL dry degassed ether was prepared. The jar was sealed with a PTFE-lined septum cap and then a second glass vial was placed in a glove box freezer for 15 minutes to cool its contents to-30 ℃. The solution of the second jar was added to the addition funnel and the contents of the addition funnel were then added dropwise to the contents of the first glass jar over a period of 10 minutes. The residual contents of the addition funnel were rinsed into the reaction mixture of the first glass jar using 2mL of diethyl ether. The resulting mixture was stirred and allowed to reach room temperature for 1.5 hours. The mixture was filtered through a PTFE frit into a clean vial to give a solution of 3-n-butylbenzylmagnesium chloride in diethyl ether. A portion of the filtrate was titrated with iodine/LiCl to determine the concentration of 3-n-butylbenzylmagnesium chloride in solution.

Preparation example 8: and (3) synthesizing tetra (3-methylbenzyl) zirconium. A40 mL oven-dried vial was charged with zirconium (IV) chloride (0.25g, 0.6mmol) and 10mL toluene under a nitrogen atmosphere in a glove box with freezer components using a PTFE-coated stir bar. The vial was sealed with a PTFE-lined septum cap and then placed in a glove box freezer for 15 minutes to cool the contents of the jar to-30 ℃. The 3-methylbenzylmagnesium chloride solution of preparation 7 (7.35mL, 2.6mmol) was added slowly, then the vial was covered with aluminum foil and the mixture was stirred while it was allowed to warm to room temperature in the dark for 16 hours. 15mL of diethyl ether was added and the mixture was filtered through celite and then the mixture was concentrated to a volume of about 2 mL. 10mL portions of pentane were added and the vial was placed in a glove box freezerOvernight. The resulting yellow precipitate was collected by filtration, and the resulting solid was then triturated in 5mL of hexane and dried three times under vacuum to remove residual THF. To the resulting solid was added 5mL of toluene, followed by filtration through a 0.45 μ M PTFE syringe filter. The filtrate was concentrated under reduced pressure, then triturated in 5mL of hexane and dried three times under vacuum. 5mL of pentane was added and the vial was placed in a glove box freezer for 72 hours. The mixture was filtered through celite and the filter cake was washed with 10mL of hexane. The filtrate was concentrated under reduced pressure to give tetrakis (3-methylbenzyl) zirconium as a yellow-brown oil.¹H NMR (400MHz, benzene-d)₆)δ7.03(t,J＝7.6Hz,1H),6.82(ddt,J＝7.5,1.8,0.9Hz,1H),6.34(dt,J＝8.0,1.4Hz,1H),6.11(d,J＝1.9Hz,1H),2.06(s,3H),1.52(s,2H)。¹³C NMR (101MHz, benzene-d)₆)δ140.90,140.02,130.97,128.68,125.92,124.99,71.42,21.68。

Bimodal test method: the presence or absence of resolved bimodality is determined by plotting dWf/dLogM (mass detector response) on the y-axis versus LogM on the x-axis to obtain a GPC chromatogram curve containing local maximum log (MW) values for the peak of the LMW polyethylene component and the peak of the HMW polyethylene component, and observing the presence or absence of a local minimum between the peak of the LMW polyethylene component and the peak of the HMW polyethylene component. dWf is the change in weight fraction, dLogM is also known as dlog (mw) and is the log change in molecular weight, and LogM is also known as log (mw) and is the log of molecular weight.

Deconvolution test method: the chromatogram obtained using the bimodality test method was divided into nine (9) Schulz-Flory molecular weight distributions. Such a deconvolution method is described in US6,534,604. Four lowest MW distributions are assigned to the LMW polyethylene component and five highest MW distributions are assigned to the HMW polyethylene component. By mathematical manipulation of the known aggregated Schulz-Flory MW distribution (Schulz-Flory MW distribution), by using the weight fractions (Wf) of the LMW polyethylene component and the HMW polyethylene component and the corresponding number average molecular weights (M)_n) And weight average molecular weight (M)_w) The sum of the values determines the LMW polyethylene component and the HMW polyethylene component in the bimodal ethylene-co-1-hexene copolymer compositionIn weight percent (wt%) for each of the plurality of the first and second compositions.

Density is measured according to ASTM D792-13, Standard Test Methods for determining Density and Specific Gravity (Relative Density) of Plastics by Displacement, method B (for testing solid Plastics in liquids other than water, e.g. liquid 2-propanol). Results are reported in grams per cubic centimeter (g/cm)³) Is a unit.

Gel Permeation Chromatography (GPC) test method: weight average molecular weight test method: m was determined using a chromatogram obtained on a high temperature gel permeation chromatograph (HTGPC, Polymer Laboratories)_wNumber average molecular weight (M)_n) And M_w/M_n. HTGPC was equipped with a transmission line, a differential refractive index Detector (DRI), and three polymer laboratory PLgel 10 μm Mixed-B columns, all contained in an oven maintained at 160 ℃. The method used a solvent consisting of BHT treated TCB, with a nominal flow rate of 1.0 milliliters per minute (mL/min), and a nominal injection volume of 300 microliters (μ L). The solvent was prepared by dissolving 6 grams of butylated hydroxytoluene (BHT, antioxidant) in 4 liters (L) of reagent grade 1,2, 4-Trichlorobenzene (TCB) and filtering the resulting solution through a 0.1 micrometer (μm) PTFE filter to give the solvent. PTFE is poly (tetrafluoroethylene). The solvent was degassed with an in-line degasser before entering the HTGPC instrument. The column was calibrated with a series of monodisperse Polystyrene (PS) standards. Separately, a known concentration of test polymer dissolved in a solvent was prepared by heating a known amount of test polymer in a known volume of solvent at 160 ℃ and shaking continuously for 2 hours to give a solution. Target solution concentration c for the test polymers was 0.5 milligrams polymer/milliliter of solution (mg/mL) to 2.0 milligrams polymer/milliliter of solution (mg/mL), with lower concentrations c being used for higher molecular weight polymers. Before running each sample, the DRI detector was purged. The flow rate in the apparatus was then increased to 1.0mL/min and the DRI detector was allowed to stabilize for 8 hours before injecting the first sample. Calculating M using a universal calibration relationship with column calibration_wAnd M_n. MW at each elution volume was calculated using the following equation:

wherein the subscript "X" represents the test sample, the subscript "PS" represents the PS standard, a_PS＝0.67、K_PS0.000175 and a_XAnd K_XObtained from published literature. For polyethylene, a_X/K_X0.695/0.000579. For polypropylene, a_X/K_X0.705/0.0002288. At each point in the resulting chromatogram, the DRI signal I from the baseline was subtracted_DRICalculating the concentration c: c is K_DRII_DRIV (dn/dc), where K_DRIFor constants determined by calibration DRI,/denotes a division, and dn/dc is the refractive index increment of the polymer. For polyethylene, dn/dc is 0.109. The polymer mass recovery is calculated from the ratio of the integrated area at the elution volume of the concentration chromatography chromatogram and the injected mass, which is equal to the predetermined concentration multiplied by the injection loop volume. All molecular weights are reported in grams per mole (g/mol) unless otherwise indicated. Additional details regarding methods for determining Mw, Mn, MWD are described in US2006/0173123, paragraphs 24-25 [0334 ]]To [0341]In (1). A plot of dW/dlog (mw) on the y-axis versus log (mw) on the x-axis gives GPC chromatograms, where log (mw) and dW/dlog (mw) are as defined above.

High Load Melt Index (HLMI) I₂₁The test method comprises the following steps: ASTM D1238-13 was used using the Standard Test Method for Melt Flow Rate of Thermoplastics for Extrusion profilometers (Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Platometer) using the conditions of 190 ℃/21.6 kilograms (kg). Results are in grams eluted per 10 minutes (g/10 minutes).

The ignition test method comprises the following steps: a40 mL glass vial was charged with a PTFE-coated magnetic stir bar and 0.16g of the spray-dried methylaluminoxane powder of preparation 1A in a glove box under a nitrogen atmosphere. To the filled vial was added 11mL of 1-octene, and the vial was then inserted into an insulated cannula mounted on a magnetic stir plate, which was rotated at a speed of about 300 revolutions per minute (rpm). To the insulated vial was added 8 micromoles (μmol) of the precatalyst (e.g., compound (1) or HN5Zr dibenzyl). The vial was capped with a rubber septum. The thermocouple probe was inserted into the vial through the rubber septum so that the tip of the thermocouple probe was below the liquid level. The temperature of the vial contents was recorded every 5 seconds until the maximum temperature was reached. The temperature and time data were downloaded into a spreadsheet and thermodynamic curves were plotted for analysis.

Melt index I₅(“I₅") test method: ASTM D1238-13 was used, using conditions of 190 ℃/5.0 kg. Results are reported in grams eluted per 10 minutes (g/10 min).

Melt flow ratio MFR5: (` I `)₂₁/I₅") test method: by adding a reagent from HLMI I₂₁Value from test method divided by melt index I₅The value of the test method.

Solubility test method: a known mass of the test precatalyst (e.g., compound (1)) and a known volume of hexane comprising at least 60 wt% n-hexane were added to a 20mL vial at room temperature and ambient pressure. A PTFE coated magnetic stir bar was added and the mixture was stirred for 1 hour, then the vial was removed from the stir plate and the mixture was allowed to stand overnight. The next day, the suspension was filtered through a 0.4 μm PTFE syringe filter into a peeled vial to give a known mass of supernatant and hexane was removed under reduced pressure to give a measurable mass of the compound of formula (1) from which the wt% solubility was calculated.

Inventive example 1(IE 1): synthesis of Compound (3a) of FIG. 3 from Compound (4) of FIG. 3 prepared according to preparation 3 (wherein each R is¹⁰Compound (3) which is a methyl group). An oven-dried 400mL glass jar was charged with a PTFE-coated magnetic stir bar, compound (4) (10g, 25.3mmol) and 200mL dry degassed n-pentane in a glove box under a nitrogen atmosphere. Then, tetrakis (dimethylamino) zirconium (IV) (6.76g, 25.3mmol) as a solid was added in small portions, and the resulting reaction was mixed at 25 deg.CThe mixture was stirred for 16 hours. The mixture was cooled in a freezer in a glove box for 1 hour to precipitate the compound (3 a). The precipitate (3a) is filtered off and the filter cake is washed with cold n-pentane. The washed compound (3a) was dried under reduced pressure to obtain 12.62g (87.1% yield) of compound (3a) as a white powder.¹H NMR (400MHz, benzene-d 6) Δ 3.37(dt,2H),3.10(d,6H),3.02(dd,3H),2.68(dq,4H),2.51(d,12H),2.20(q,18H),2.14(s,7H),1.84(s, 1H); 13C NMR (101MHz, benzene-d 6) delta 149.77,132.34,132.14,130.04,129.98,129.32,56.29,48.86,44.35,40.91,17.31,17.27,16.72,16.65, 16.09.

Inventive example 2(IE 2): compound (2a) of FIG. 3 (compound (2) in which M is Zr and each X is Cl) was synthesized from compound (3a) of FIG. 3. An oven-dried 400mL glass jar was charged with a PTFE-coated magnetic stir bar, compound (3a) (12.62g, 22.0mmol), and 250mL dry degassed ether in a glove box under a nitrogen atmosphere. Chlorotrimethylsilane (6.2mL, 48.5mmol) was added and the mixture was stirred at 25 ℃ for 24 h. The mixture was cooled in a glove box freezer for 1 hour to precipitate the compound (2 a). The precipitate (2a) was collected by filtration and the filter cake was washed with cold n-pentane. The washed (2a) was dried under reduced pressure to obtain 10.77g (88.0% yield) of the compound (2a) as a white powder, i.e., bis (2- (pentamethylphenylamido) ethyl) -amine zirconium (IV) dichloride.¹H NMR (400MHz, benzene-d 6) Δ 3.40(dt,1H),2.95(dt,1H),2.59(dp,2H),2.49(s,3H),2.46(s,3H), 2.43-2.34 (m,1H),2.13(s,3H),2.06(s,3H),2.04(s, 3H). 13C NMR (101MHz, chloroform-d 6) delta 145.64,133.37,133.20,132.61,129.84,129.57,57.69,48.97,17.03,17.01,16.70, 16.47.

Inventive example 3(IE 3): synthesis of Compound (1A) of FIG. 2 (wherein M is Zr and each R is CH) from Compound (2a) of FIG. 3₂Si(CH₃)₃Compound (1)) of (1). An oven-dried 400mL glass jar was charged with a PTFE-coated magnetic stir bar, compound (2a) (5.0g, 9.0mmol), and 250mL of dry degassed toluene in a glove box under a nitrogen atmosphere. A1.0M solution of trimethylsilylmethylmagnesium chloride in hexane was added, and the reaction mixture was stirred at 25 ℃ for 23 hours. Quench the reaction mixture with 2mL 1, 4-dioxane and then let it inThe quenched mixture was filtered through celite. The filtrate was concentrated under reduced pressure. The residual concentrate was triturated in 20mL of hexane and the remaining triturated material was dried under reduced pressure. The grinding/drying was repeated twice. The resulting light orange solid was slurried in 200mL of hexane and then placed in a glove box freezer for several hours. The resulting fine precipitate was filtered off through celite, and the filtrate was concentrated under reduced pressure and dried in vacuo to give compound (1A) as a pale orange powder. Compound (1A) is bis (2- (pentamethylphenylamido) ethyl) -amine zirconium (IV) bis-trimethylsilylmethyl. The procedure of IE3 was repeated twice to give 14.2g (79.8% average yield from three runs) of compound (1A) combined.¹H NMR (400MHz, benzene-d 6) δ 3.38(dt, J ═ 12.6,5.4Hz,2H),3.14(ddd, J ═ 12.3,6.7,5.3Hz,2H), 2.69-2.62 (m,3H),2.60(s,8H),2.44(s,6H),2.22(s,6H),2.17(s,6H),2.10(s,7H), 1.25-1.19 (m,1H), 0.42-0.38 (m,2H),0.24(s,9H), -0.12(s,2H), -0.28(s, 9H). 13C NMR (101MHz, benzene-d 6) delta 147.18,133.07,132.73,130.97,129.74,129.67,57.49,55.96,54.74,48.29,16.80,16.70,16.67,16.37,16.23,3.40, 2.02. The light-off performance was measured according to the light-off test method and measured according to the solubility test method. The solubility and time to maximum temperature results are reported in table 1 below.

Inventive example 4(IE 4): synthesis of Compound (1B) of FIG. 2 (wherein M is Zr and each R is CH) from Compound (2a) of FIG. 3₂- (1, 4-phenylene) -C (CH)₃)₃Compound (1)) of (1). A clean oven-dried wide mouth was charged with a PTFE-coated magnetic stir bar, compound (2a) (1.5g, 2.69mmol) and 100mL of dry degassed toluene to make a toluene solution of compound (2 a). The jar was placed in a glove box freezer for 15 minutes together with a separate bottle containing the 4-tert-butylbenzylmagnesium chloride solution of preparation 4 to cool to-30 ℃. The 4-tert-butylbenzylmagnesium chloride solution was then added to the addition funnel, and the contents of the addition funnel were added dropwise to the solution of compound (2 a). The mixture was stirred and allowed to reach room temperature over 1 hour (r.t.). Then 0.5mL of 1, 4-dioxane was added and the resulting mixture was filtered through celite. The filtrate was concentrated under reduced pressure, and the resulting residue was taken up in 30mL of toluene. Filtering again and concentrating under reduced pressure to obtainThe residue of two filtrations/concentrations. The residue was triturated with three 10mL portions of hexane and the triturated residue was dried under reduced pressure to ensure complete removal of the toluene. To the residue was added 20mL of pentane, and the resulting mixture was placed in a glove box freezer for 72 hours to give a yellow precipitate, which was collected by filtration through a cooled PTFE frit and dried under reduced pressure to give 0.95g of compound (1B) (45% yield).¹H NMR (400MHz, benzene-d)₆)δ7.31–7.23(m,2H),7.18–7.07(m,4H),5.73–5.66(m,2H),3.45(dt,J＝11.8,5.5Hz,2H),3.25(dd,J＝9.8,4.5Hz,1H),3.15(dt,J＝12.0,5.7Hz,2H),2.76–2.65(m,2H),2.49(d,J＝4.4Hz,13H),2.28(s,6H),2.14(d,J＝18.8Hz,11H),1.77(s,2H),1.33(s,8H),1.21(s,8H),0.87(s,2H)。¹³C NMR (101MHz, benzene-d)₆) δ 152.70,148.52,147.67,142.21,136.97,133.69,132.32,131.19,130.57,130.41,129.41,126.93,125.50,124.38,63.41,58.04,53.38,49.37,34.13,34.08,31.90,31.88,17.18,17.14,17.06,16.68, 16.61. The light-off performance was measured according to the light-off test method and measured according to the solubility test method. The solubility and time to maximum temperature results are reported in table 1 below.

Inventive example 5(IE 5): synthesis of Compound (1C) of FIG. 2 (wherein M is Zr and each R is CH) from Compound (2a) of FIG. 3₃Compound (1)) of (1). An oven-dried 100mL glass jar was charged with a PTFE-coated magnetic stir bar, compound (2a) (0.5g, 0.9mmol) and 25mL dry degassed dichloromethane in a glove box under a nitrogen atmosphere. The mixture was placed in a glove box freezer for 1 hour to cool to-30 ℃. A3.0M solution of methylmagnesium bromide in ether (0.6mL, 1.8mmol) was added slowly with stirring, and the mixture was then warmed to room temperature and stirred for 30 minutes. The mixture was quenched with 0.2mL of 1, 4-dioxane, then filtered through PTFE, and the filtrate was concentrated under reduced pressure. The residue was triturated in 20mL of n-pentane and the resulting solid was filtered. The solid was dried under reduced pressure to give 0.32g (69% yield) of compound (1B) as a pale orange powder.¹H NMR (400MHz, benzene-d)₆)δ3.40(ddd,J＝12.3,8.9,5.5Hz,3H),3.11(ddd,J＝12.3,5.2,3.3Hz,2H),2.51(s,7H),2.49(s,7H),2.47–2.42(m,5H),2.21(s,6H),2.18(s,7H),2.11(s,7H),0.17(s,3H),0.07(s,3H)。The light-off performance was measured according to the light-off test method and measured according to the solubility test method. The solubility and time to maximum temperature results are reported in table 1 below.

Inventive example 5A (IE 5A): synthesis of Compound (1D) (wherein M is Zr and each R is CH) from Compound (2a)₂- (1, 3-phenylene) -CH₂CH₂CH₂CH₃Compound (1)

(2a) (1D). A clean oven-dried wide mouth was charged with a PTFE-coated magnetic stir bar, compound (2a) (0.4g, 0.7mmol), and 20mL of dry degassed toluene to make a toluene solution of compound (2 a). The jar was placed in a glove box freezer for 15 minutes together with a separate bottle containing the 3-n-butylbenzylmagnesium chloride solution of preparation example 7 to cool to-30 ℃. The 3-n-butylbenzylmagnesium chloride solution was then added to the addition funnel, and the contents of the addition funnel were added dropwise to the solution of compound (2 a). The mixture was stirred and allowed to reach room temperature over 16 hours (r.t.). Then 20mL of diethyl ether was added and the resulting mixture was filtered through celite. The filtrate was concentrated under reduced pressure, and the resulting residue was taken up in 30mL of toluene. Again filtered through celite and concentrated under reduced pressure to give a twice filtered/concentrated residue. The residue was triturated with three 10mL portions of hexane and the triturated residue was dried under reduced pressure to ensure complete removal of the toluene. To the residue was added 20mL of pentane, and the resulting mixture was placed in a glove box freezer for 72 hours to give a yellow precipitate, which was collected by filtration through a cooled PTFE frit and dried under reduced pressure to give 0.12g of compound (1D) (22% yield).¹H NMR (400MHz, benzene-d)₆)δ7.21(t,J＝7.4Hz,1H),7.08–7.01(m,2H),6.88(t,J＝7.5Hz,1H),6.81(dt,J＝7.6,1.4Hz,1H),6.76–6.71(m,1H),5.58–5.51(m,2H),3.48(dt,J＝11.8,5.6Hz,2H),3.34(s,1H),3.19(dt,J＝12.1,5.8Hz,2H),2.73(dq,J＝12.2,6.0Hz,3H),2.61(td,J＝7.5,6.9,4.0Hz,5H),2.48(d,J＝5.8Hz,10H),2.27(s,6H),2.15(s,7H),2.11(s,7H),1.83(s,2H),1.72–1.61(m,3H),1.44–1.35(m,3H),1.31(dd,J＝14.8,7.4Hz,3H),0.93(s,2H),0.93–0.86(m,3H)。¹³C NMR (101MHz, benzene-d)₆) δ 147.35,146.46,142.43,133.37,132.09,131.93,130.96,130.25,130.11,124.83,123.77,121.68,119.94,63.63,57.68,53.33,49.12,36.11,36.07,32.67,22.32,16.82,16.78,16.70,16.35,16.29, 13.79. The light-off performance was measured according to the light-off test method and measured according to the solubility test method. The solubility and time to maximum temperature results are reported in table 1 below.

Inventive example 5B (IE 5B): synthesis of Compound (1E) (wherein M is Zr and each R is CH) from Compound (4)₂- (1, 3-phenylene) -CH₃Compound (1)

(4) (1E). A clean oven-dried 40mL vial was charged with a PTFE-coated magnetic stir bar, the tetrakis (3-methylbenzyl) zirconium of preparation 8 (0.12g, 0.2mmol), and 5mL of dry degassed toluene. Compound 4 was added as a solid to the vial, and the mixture was stirred at room temperature for 2 hours. To the mixture was added 30mL of pentane and the off-white solid was collected by filtration, then the solid was washed with 10mL of cold pentane to give 88mg of compound (1E) (53.4% yield).¹H NMR (400MHz, benzene-d)₆)δ7.25–7.10(m,1H),7.05–6.98(m,2H),6.86–6.70(m,3H),5.50(d,J＝7.8Hz,1H),5.44(s,1H),3.53–3.40(m,2H),3.29–3.20(m,1H),3.15(dt,J＝12.0,5.8Hz,2H),2.69(q,J＝6.1,5.5Hz,3H),2.57(td,J＝10.9,5.3Hz,2H),2.47(s,6H),2.42(s,6H),2.29(s,3H),2.24(s,7H),2.15(s,7H),2.10(s,7H),1.98(s,3H),1.78(s,2H),0.91–0.83(m,0H),0.87(s,2H)。¹³C NMR (101MHz, benzene-d)₆) δ 147.27,141.46,137.28,133.33,132.11,131.90,130.95,130.22,130.14,125.71,124.35,121.30,120.39,63.48,57.66,53.13,49.13,21.59,16.77,16.71,16.34, 16.27. The light-off performance was measured according to the light-off test method and measured according to the solubility test method. The solubility and time to maximum temperature results are reported in table 1 below.

Inventive example 6A (IE 6A): a monomodal catalyst system was prepared from compound (1A) and the activator. The slurry activator formulation of preparation example 1B was fed separately through the catalyst injection line and the freshly prepared pre-catalyst system of IE3 was fed through the different catalyst injection lines into an in-line mixer where they were contacted with each other to give a unimodal catalyst system which then flowed into the reactor through the injection line.

Inventive examples 6B and 6C (prophetic, IE6B and IE 6C): the procedure of IE6A was repeated, except that compound (1A) was replaced by compound (1B) of IE4 or compound (1C) of IE5, to give a monomodal catalyst system prepared from compound (1B) or (1C), respectively.

Inventive example 6D (IE 6D): the procedure of IE6A was repeated except that the freshly prepared compound (1A) (wherein M is Zr and each R is CH) was used₂Si(CH₃)₃The compound (1)) of (1) and a freshly prepared hexane solution of Methylaluminoxane (MAO). Different (1A) solutions were prepared by dissolving a measured amount of compound (1A) in separate hexane aliquots to give 700mL of a 0.91 wt% solution of compound (1A) in hexane, 700mL of a 1.18 wt% solution of compound (1A) in hexane, and 550mL of a 0.91 wt% solution of compound (1A) in hexane, respectively. The solution need not be cooled but can be transported or stored at 25 ℃. The activator solutions were fed separately through the catalyst injection pipes and the freshly prepared compound (1A) solution was fed through the different catalyst injection pipes into an in-line mixer where they contacted each other to give a solution of the monomodal catalyst system, which then flowed into the reactor through the injection pipes.

Inventive examples 6E and 6F (prophetic, IE6E and IE 6F): the procedure of IE6D was repeated, except that compound (1A) was replaced by compound (1B) of IE4 or compound (1C) of IE5, to give a monomodal catalyst system prepared from compound (1B) or (1C), respectively.

Inventive example 6F (IE 6G): the procedure of IE6A was repeated except that the freshly prepared compound (1A) (wherein M is Zr and each R is CH) was used₂Si(CH₃)₃Compound (1)) and a freshly prepared hexane solution of Methylaluminoxane (MAO). By mixing measured amount of IE3Compound (1A) was added to a 106 liter (L) graduated cylinder containing hexane to prepare different solutions of (1A). To the graduated cylinder was added 11.3 kilograms (kg) of high purity isopentane to give a pre-catalyst formulation of 0.10 weight percent solution of compound (1A) in hexane/isopentane mixture. The solution need not be cooled but can be transported or stored at 25 ℃. The activator solutions were fed separately through the catalyst injection pipes and the freshly prepared compound (1A) solution was fed through the different catalyst injection pipes into an in-line mixer where they contacted each other to give a solution of the monomodal catalyst system, which then flowed into the reactor through the injection pipes.

Inventive examples 6H and 6I (prophetic, IE6H and IE 6I): the procedure of IE6G was repeated, except that compound (1A) was replaced by compound (1B) of IE4 or compound (1C) of IE5, to give a monomodal catalyst system prepared from compound (1B) or (1C), respectively.

Inventive example 7A (IE 7A): a bimodal catalyst system was prepared comprising an alkane-soluble non-metallocene catalyst prepared from compound (1A) and a metallocene catalyst prepared from (MeCp) (1, 3-dimethyl-4, 5,6, 7-tetrahydroindenyl) ZrMe2, wherein Me is methyl, Cp is cyclopentadienyl, and MeCp is methylcyclopentadienyl. The spray-dried metallocene was fed separately with the activator formulation of preparative example 2 through a catalyst injection pipe and the pre-catalyst formulation of compound (1A) of IE5 was fed into an in-line mixer through different catalyst injection pipes, where the feeds contacted each other to form a catalyst system, which then flowed into the reactor through the injection pipes.

Inventive examples 7B to 7I (prophetic, IE7B to IE 7I): the procedure of IE7A was repeated except that the spray-dried metallocene and the activator formulation of preparation example 2 were replaced with the catalyst formulation of any one of IE6B to IE6I to give a bimodal catalyst system comprising an alkane-soluble non-metallocene catalyst, an activator and a metallocene catalyst prepared from (MeCp) (1, 3-dimethyl-4, 5,6, 7-tetrahydroindenyl) ZrMe 2.

Inventive example 8A (IE 8A): copolymerisation of ethylene and 1-hexene with a monomodal catalyst system of IE6A prepared from Compound (1A) to prepare a monomodal poly (ethylene-co-1-hexene) copolymerisationA compound (I) is provided. For each run, a gas-phase fluidized-bed reactor having an internal diameter of 0.35m and a bed height of 2.3m and a fluidized bed consisting essentially of polymer particles were used. The fluidizing gas is passed through the bed at a velocity of from 0.51 meters per second (m/s) to 0.58 m/s. The effluent gas is discharged from the top of the reactor and passed through a recycle gas line with a recycle gas compressor and heat exchanger before re-entering the reactor below the distribution grid. The fluidized bed temperature was maintained at a constant value of 105 ℃ by continuously adjusting the temperature and/or flow rate of the cooling water for temperature control. Gaseous feed streams of ethylene, nitrogen and hydrogen, and 1-hexene comonomer were introduced into the recycle gas line. The reactor was operated at a total pressure of 2410 kilopascal gauge (kPa gauge). The reactor was vented to a flare to control the total pressure. The respective flow rates of ethylene, nitrogen, hydrogen and 1-hexene were adjusted to maintain the gas composition target. The ethylene partial pressure was set to 1.52 megapascals (MPa). 1-hexene/ethylene (C)₆/C₂) The molar ratio was set to 0.0050, and hydrogen/ethylene (H) was added₂/C₂) The molar ratio was set to 0.0020. The ICA (isopentane) concentration was maintained at 8.5 mol% to 9.5 mol%. The concentration of all gases was measured using an on-line gas chromatograph. The freshly prepared unimodal catalyst system of IE6A was fed to the polymerization reactor at a rate sufficient to maintain a poly (ethylene-co-1-hexene) copolymer productivity of about 13 kg/hr to 16 kg/hr while also controlling the feed rate to achieve a loading of 50 micromoles of zirconium per gram of spray dried solid. Poly (ethylene-co-1-hexene) copolymers ("resins") are characterized by a monomodal molecular weight distribution, a high load melt index (HLMI or I)₂₁) 0.21g/10 min, density 0.9311g/cm³Number average molecular weight (M)_n) A weight average molecular weight (M) of 79,727_w) Is 610,319, z average molecular weight (M)_z) Is 3,197,212, and has a molecular weight distribution (M)_w/M_n) It was 7.66. IE8A produced a unimodal high molecular weight copolymer using a unimodal catalyst system comprising an activator formulation comprising no precatalyst and a precatalyst formulation comprising a precatalyst (1) comprising no activator. The resin particle size and particle size distribution data are shown in table 2 below.

Inventive examples 8B to 8I (prophetic, IE8B to IE 8I): the procedure of IE8A was repeated except that the unimodal catalyst system of IE6A was replaced by a different unimodal catalyst system of IE6B to IE6I, respectively, to give a unimodal poly (ethylene-co-1-hexene) copolymer.

Inventive example 9A (IE 9A): ethylene and 1-hexene were copolymerized using a bimodal catalyst system prepared from compound (1A) and a metallocene to produce a bimodal poly (ethylene-co-1-hexene) copolymer. The polymerization step of IE8A was repeated except that instead of feeding the unimodal catalyst system of IE6A, the bimodal catalyst system of IE7A was fed into the reactor. Adjusting the ratio of compound (1A) feed to spray-dried metallocene slurry to adjust the high load melt index (I) of the bimodal poly (ethylene-co-1-hexene) copolymer in the reactor₂₁) The adjustment was about 6g/10 min. C is to be₆/C₂The molar ratio was increased to 0.0060 to reduce the density of the bimodal poly (ethylene-co-1-hexene) copolymer. The feed rate of the spray-dried metallocene slurry and the solution of compound (1A) was adjusted to a rate sufficient to maintain a production rate of the bimodal poly (ethylene-co-1-hexene) copolymer of about 13 kg/hour to 16 kg/hour. The bimodal poly (ethylene-co-1-hexene) bimodal copolymer produced is bimodal, its I₂₁6.1g/10 min, melt flow ratio (I)₂₁/I₅) Is 28.9, and has a density of 0.9476g/cm³，M_nIs 19,194, M_wIs 353,348, M_zIs 2,920,833, and M_w/M_nWas 18.41. The bimodality of the bimodal poly (ethylene-co-1-hexene) copolymer of IE9A is illustrated by the GPC diagram shown in fig. 1. The resin particle size and particle size distribution data are shown in table 2 below.

Inventive examples 9B to 9I (prophetic, IE9B to IE 9I): the procedure of IE9A was repeated except that the bimodal catalyst systems of any one of IE7B to IE7I, respectively, were used to give the corresponding bimodal poly (ethylene-co-1-hexene) copolymers.

Comparative example 1(CE 1): the synthesis of [ N '- (2,3,4,5, 6-pentamethylphenyl) -N- [2- (2,3,4,5, 6-pentamethylphenyl) amino- κ N ] ethyl ] -1, 2-ethane-diamino (2-) κ N, κ N' ] zirconium dichloride (abbreviated herein as "HN 5Zr dichloride") is described in US6967184B 2. The light-off performance was measured according to the light-off test method. The time to maximum temperature results are reported in table 1 below.

Comparative example 2(CE 2): the synthesis of bis (benzyl) [ N '- (2,3,4,5, 6-pentamethylphenyl) -N- [2- (2,3,4,5, 6-pentamethylphenyl) amino- κ N ] ethyl ] -1, 2-ethane-diamino (2-) κ N, κ N' ] zirconium (herein abbreviated as "HN 5Zr dibenzyl") can be accomplished by reacting HN5Zr dichloride of CE1 with two molar equivalents of benzylmagnesium chloride under anhydrous tetrahydrofuran conditions. The light-off performance was measured according to the light-off test method and measured according to the solubility test method. The solubility and time to maximum temperature results are reported in table 1 below.

Comparative example 3(CE 3): ethylene and 1-hexene were copolymerized using a comparative unimodal catalyst system prepared from HN5Zr dibenzyl of CE2 in a spray dried formulation with hydrophobic fumed silica and MAO to prepare a comparative unimodal poly (ethylene-co-1-hexene) copolymer. The procedure of IE8A was replicated except that a comparative unimodal catalyst system was used instead of the unimodal catalyst system of IE 6A. Comparative poly (ethylene-co-1-hexene) copolymers characterized by a monomodal molecular weight distribution, high load melt index (HLMI or I)₂₁) 0.20g/10 min and a density of 0.9312g/cm³. The resin particle size and particle size distribution are shown in table 2 below.

Table 1: solubility in hexane comprising at least 60 wt% n-hexane and light-off properties in the polymerization of 1-octene.

The solubility of compound (1A) in hexane comprising at least 60 wt.% n-hexane is at least 23.3 wt.%, measured according to the solubility test method. Unexpectedly, the solubility of compound (1A) in hexane was 700 to 800 times greater than the solubility of HN5Zr dibenzyl (CE2) in hexane.

In the light-off test method, the time for the compound (1A) to reach the highest temperature was 1.3 minutes. Unexpectedly, compound (1A) reached the highest temperature 4 times longer than HN5Zr dichloride (CE1) and 60 to 61 times longer than HN5Zr dibenzyl (CE 2).

As shown by the data in table 1, the compound (1) has a significantly improved solubility in alkanes, which reduces the complexity of the transition between catalyst systems, and a significantly higher light-off performance than the comparative precatalyst HN5Zr dibenzyl, which reduces fouling of the distribution plates in the gas phase polymerization reactor. Thus, compound (1) solves the above-mentioned problems of the prior non-MCN precatalysts.

Table 2: average particle size and particle size distribution of IE8A and IE 9A.

In table 2, aps (mm) is the average particle size in millimeters. As shown by the data in table 2, the average particle size of the particles of the unimodal poly (ethylene-co-1-hexene) copolymer of IE8A was 32 times the average particle size of the particles of the comparative unimodal poly (ethylene-co-1-hexene) copolymer of CE 3. The average particle size of the particles of the inventive bimodal poly (ethylene-co-1-hexene) copolymer of IE9A was 15 times the APS of the particles of the comparative unimodal poly (ethylene-co-1-hexene) copolymer of CE 3.

In Table 2, the bottom collector collects all particles that pass through a 0.074mm (200 mesh) screen. The percentage of fines was equal to the sum of the wt% of the particles captured by the 0.074mm (200 mesh) sieve and the wt% of the particles passing through the 0.074mm (200 mesh) sieve and collected in the bottom head. The percent fines of the comparative unimodal poly (ethylene-co-1-hexene) copolymer of CE3 was 4 times the percent fines of the inventive unimodal poly (ethylene-co-1-hexene) copolymer of IE 8A.

Claims (13)

1.A process for polymerizing olefin monomers to produce a first polyolefin composition comprising a first polyolefin polymer, the process comprising steps (a) to (C): (A) contacting a solution of a first alkane-soluble non-metallocene pre-catalyst dissolved in an alkane solvent with an activator to produce a first trim catalyst comprising a first alkane-soluble non-metallocene catalyst; (B) feeding the first trim catalyst to a polymerization reactor; and (C) polymerizing the olefin monomer with the first trim catalyst in the polymerization reactor; thereby producing the first polyolefin composition comprising the first polyolefin polymer; wherein the first alkane-soluble non-metallocene pre-catalyst is characterized by a solubility in hexane comprising at least 60 wt.% n-hexane of at least 0.10 wt.% based on the total weight of the first alkane-soluble non-metallocene pre-catalyst and hexane, as measured using the solubility test method.

2. The method of claim 1, wherein the first trim catalyst comprises a solution of the first alkane-soluble non-metallocene catalyst dissolved in an alkane solvent, and step (B) comprises feeding the solution into the reactor, the solution being free of support material.

3. The method of claim 1 or 2, further comprising steps (a) and (b): (a) separately from step (a), contacting a first metallocene precatalyst with an activator and optionally a support material, in order to prepare a first metallocene catalyst, said first metallocene catalyst optionally being free of said support material or being located on and/or in said support material; and (B) feeding the first metallocene catalyst to the polymerization reactor separately from step (B); and wherein step (C) further comprises polymerizing the olefin monomer with the first metallocene catalyst in the polymerization reactor; thereby preparing a first bimodal polyolefin composition comprising the first polyolefin polymer and a second polyolefin polymer.

4. The method of claim 3, wherein step (B) comprises feeding the first trim catalyst into the polymerization reactor as a solution of the first alkane-soluble non-metallocene catalyst dissolved in a first alkane solvent; and wherein said step (b) comprises separately feeding a solution of said first metallocene catalyst dissolved in a second alkane solvent to said polymerization reactor; wherein the first alkane solvent is the same or different from the second alkane solvent; and wherein the solution is free of a support material.

5. The method of claim 3 or 4, further comprising, after the step (C), (D) transitioning the method from the steps (a) and (b) to steps (a1) and (b1), respectively: (a1) contacting a second metallocene precatalyst, which is different in the structure of at least one cyclopentadienyl ligand from the first metallocene precatalyst, with an activator and optionally a support material in order to prepare a second metallocene catalyst, which is different from the first metallocene catalyst, wherein the second metallocene catalyst is free of support material or is located on and/or in the support material; and (b1) decreasing the feed of the first metallocene catalyst from a steady state value until the first metallocene catalyst is no longer fed to the polymerization reactor, and independently starting and increasing the feed of the second metallocene catalyst to the polymerization reactor until the second metallocene catalyst is fed to the polymerization reactor at a steady state value; and wherein step (C) further comprises polymerizing the olefin monomer with the second metallocene catalyst in the polymerization reactor; thereby producing a second multimodal polyolefin composition comprising the first polyolefin polymer produced by the first trim catalyst and a third polyolefin polymer produced by the second metallocene catalyst, wherein the third polyolefin polymer is different from each of the first and second polyolefin polymers.

6. The method of claim 1, wherein the first trim catalyst further comprises a support material having the first alkane-soluble non-metallocene catalyst disposed thereon.

7.A process for polymerizing olefin monomers to produce a first bimodal polyolefin composition comprising a first Higher Molecular Weight (HMW) polyolefin component and a first Lower Molecular Weight (LMW) polyolefin component, the process comprising steps (1) to (5): (1) contacting a solution of a first alkane-soluble non-metallocene pre-catalyst dissolved in an alkane solvent with an activator to produce a first trim catalyst comprising a first alkane-soluble non-metallocene catalyst; (2) contacting a first metallocene pre-catalyst and an additional amount of the first alkane-soluble non-metallocene pre-catalyst with an activator and optionally a support material to produce a first bimodal catalyst system comprising a first metallocene catalyst and an additional amount of the first alkane-soluble non-metallocene catalyst, the first bimodal catalyst system optionally being free of or located on and/or in the support material; (3) contacting the first bimodal catalyst system with the first trim catalyst to produce a first mixed catalyst system comprising a mixture of the first bimodal catalyst system and the first trim catalyst; (4) feeding the first mixed catalyst system to a polymerization reactor; and (5) polymerizing the olefin monomer with the first mixed catalyst system in the polymerization reactor; thereby producing the first HMW polyolefin component and the first LMW polyolefin component of the first bimodal polyolefin composition; wherein the first ASNM precatalyst is characterized by a solubility in hexane comprising at least 60 wt.% n-hexane of at least 0.10 wt.%, based on the total weight of the first ASNM precatalyst and hexane, as measured using the solubility test method.

8. The method of claim 7, further comprising, after step (5), (6) transitioning the method from steps (2) to (5) to steps (2a) to (5a), respectively: (2a) contacting a second metallocene precatalyst and a second additional amount of the first alkane-soluble non-metallocene precatalyst with an activator and optionally a support material, so as to prepare a second bimodal catalyst system comprising the second metallocene catalyst and the second additional amount of the first alkane-soluble non-metallocene catalyst, the second bimodal catalyst system optionally being free of or located on and/or in the support material; (3a) contacting the second bimodal catalyst system with the same trim catalyst of step (1) to produce a second mixed catalyst system comprising a mixture of the second bimodal catalyst system and the first trim catalyst; (4a) decreasing the feed of the first mixed catalyst system from a steady state value until the first mixed catalyst system is no longer fed to the polymerization reactor, and independently starting and increasing the feed of the second mixed catalyst system to the polymerization reactor until the second mixed catalyst is fed to the polymerization reactor at a steady state value; and (5a) polymerizing the olefin monomer with the second mixed catalyst system in the polymerization reactor; thereby producing a second bimodal polyolefin composition comprising the first HMW polyolefin component and a second LMW polyolefin component, the second LMW polyolefin component being different from each of the first HMW polyolefin component and the first LMW polyolefin component.

9. The method of any one of claims 1 to 8, wherein the olefin monomer is any one of (i) to (vii): (i) ethylene; (ii) propylene; (iii) (C)₄-C₂₀) An alpha-olefin; (iv)1, 3-butadiene; (v) (iii) a combination of (i) and (ii); (vi) (iv) a combination of (i) and (iii); and (vii) combinations of (i), (ii), and (iv); and wherein the first polyolefin polymer or the HMW polyolefin component comprises any one of (a) to (g): (a) a polyethylene homopolymer; (b) a polypropylene homopolymer; (c) poly (C)₄-C₂₀) An alpha-olefin polymer; (d) a polybutadiene polymer; (e) ethylene-propylene copolymers; (f) poly (ethylene-co- (C)₄-C₂₀) Alpha-olefin) copolymers; and (g) an ethylene-propylene-butadiene copolymer.

10. The method of any one of claims 1 to 9, wherein the first polyolefin polymer or the HMW polyolefin component has a weight average molecular weight of at least 110,000 grams per mole (g/mol).

11. The process of any one of claims 1 to 10, wherein the polymerization is a gas phase polymerization process and the reactor is a single gas phase polymerization reactor.

12. The method of any one of claims 1 to 11, further comprising transitioning from step (B) to step (B1): feeding a second trim catalyst to the polymerization reactor, the second trim catalyst prepared by contacting a solution of a second alkane-soluble non-metallocene pre-catalyst dissolved in an alkane solvent with an activator to produce a second alkane-soluble non-metallocene catalyst; wherein the second alkane-soluble non-metallocene precatalyst is different from the first alkane-soluble non-metallocene precatalyst in the structure of at least one non-metallocene ligand, and the second alkane-soluble non-metallocene catalyst is different from the first alkane-soluble non-metallocene catalyst in the structure of at least one non-metallocene ligand; wherein the second alkane-soluble non-metallocene precatalyst is characterized by a solubility in hexane comprising at least 60 weight percent n-hexane of at least 0.10 weight percent, based on the total weight of the second alkane-soluble non-metallocene precatalyst and hexane, as measured using the solubility test method; and wherein the transitioning comprises decreasing the feed of the first trim catalyst from a steady state value until the first trim catalyst is no longer fed into the polymerization reactor, and independently starting and increasing the feed of the second trim catalyst into the polymerization reactor until the second trim catalyst is fed into the polymerization reactor at a steady state value.

13. The method of any of claims 1 to 12, wherein the first alkane-soluble non-metallocene precatalyst and any second alkane-soluble non-metallocene precatalyst are independently characterized as comprising at least 60 weight percent n-hexane (CH), based on their total weight₃(CH₂)₄CH₃) Has a solubility in hexane of 0.50 to 24 wt%.

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